Expanded olefin polymer
A thermoplastic synthetic resin such as polyethylene or ethylene-vinyl acetate copolymer resin containing 0.1 to 10 wt. % of a specific additive selected from specific classes of compounds, namely saturated higher fatty acid amides, saturated higher aliphatic amines and complete esters of saturated higher fatty acids is found to be very suitable for production of expanded articles and can be easily formed into expanded articles with little shrinkage after expansion, free from creases on the surface or cracks on the cell walls, and having excellent characteristics such as good closed cellular characteristic, high compressive strength, low density, etc.
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This invention relates to a novel thermoplastic synthetic resin composition suitable for manufacturing expanded products of various kinds, which contains at least one compound selected from specific classes of compounds. This invention relates also to a process for expanding such a novel thermoplastic synthetic resin composition and to expanded products of a polyolefin resin obtained by such a process having excellent characteristics.
A thermoplastic synthetic resin of which expansion molding is difficult, for example, a polyolefin resin is known to be inferior in retentivity of gases such as of blowing agents as compared with such a resin as polystyrene resin.
Typical well-known methods of prior art for improvement of expandability of polyolefin resins may be classified broadly into four methods as follows:
(1) A method as disclosed by Japanese published examined patent applications No. 8840/1965 and No. 6278/1966, wherein the starting resin is subjected to crosslinking;
(2) A method as disclosed by U.S. Pat. No. 3,810,964, wherein the starting resin is mixed with a resin other than polyolefin resins;
(3) A method as disclosed by Japanese published examined patent applications No. 4341/1960 and No. 19628/1972, wherein there is employed a blowing agent with a composition and components specifically selected; and
(4) A method as disclosed by Japanese published examined patent applications No. 43997/1971 and No. 43998/1971, wherein there is added in the starting resin a partial ester of a specific polyhydric alcohol.
These methods, however, involve a number of drawbacks and none of them are satisfactory in commercial application. For example, according to the method (1), rheological flow properties of the resin can be improved, whereby it is possible to control resin temperature conditions optimum for melt-flow viscosity suitable for expansion. However, the temperature control range can be improved only to a small extent and besides there is no improvement of retentivity of gases such as blowing agents at all. Thus, this method fails to give substantial improvement in the art. That is, even if expansion may proceed as intended, the resultant expanded product will suffer from immediate shrinkage to be converted directly to expanded products with high density. Alternatively, even if the once shrinked expanded product may have a chance to be expanded again by the air impregnated thereinto, the creases, concavo-convex deformations on the surface or cracks on cell walls formed at the time of shrinkage cannot thereby be remedied. In consequence, no excellent expanded product can be obtained. For the same reason as mentioned above in connection with the method (1), the method (2) cannot be free from the same drawback. In addition it further involves the drawback that the desirable characteristics inherent in a polyolefin resin may be impaired. The method (3), especially that as disclosed by Japanese published examined patent application No. 4341/1960, is now accepted as the most excellent method and has been practically used for commercial production of thick expanded articles. But this method cannot also be free from the problem of shrinkage or concavo-convex deformations on the surface of the expanded products. Furthermore, the specific blowing agents to be employed in this method are too expensive to be economical. Lastly, the partial esters used in the method (4) have insufficient effect of preventing shrinkage or cannot sufficiently be kneaded with the resin, whereby expansion moldability is lowered.
An object of the present invention is to provide a resin composition which can readily be formed into an expanded product with good quality from a synthetic resin which itself is difficultly formed into an expanded product with good quality due to excessive shrinkage phenomenon, particularly a polyolefin resin composition suitable for preparation of expanded products having a bulk density of 10 to 200 kg/m.sup.3 and smooth surface, and being excellent in closed cellular structure as well as in compressive strength.
Another object of the present invention is to provide a novel expanded product of a polyolefin resin having specific characteristics of an expanded product which cannot be obtained by any of prior art methods.
Still another object of the present invention is to provide a process for expansion of a thermoplastic resin which is capable of supplying economically expanded articles with low density, high closed cell percentage having excellent surface smoothness and compressive strength by preventing shrinkage in volume of the expanded products with lapse of time.
According to the present invention, there is provided a thermoplastic resin composition for manufacturing expanded products, comprising a thermoplastic synthetic resin and at least one compound selected from the group consisting of the compounds represented by the formulas (I), (II) and (III) as set forth below contained in said resin in an amount of 0.1 to 10% by weight based on the weight of said resin: ##STR1## wherein R.sub.1 is an alkyl group having 10 to 24 carbon atoms, X and X' each hydrogen atom, an alkyl group having 1 to 24 carbon atoms which may be substituted or a substituent containing a group of the formula --(R.sub.4 O).sub.m -- wherein R.sub.4 is an alkylene group having 1 to 5 carbon atoms and m an integer of 1 to 10; ##STR2## wherein R.sub.2 is an alkyl group having 9 to 23 carbon atoms, Y and Y' each hydrogen atom, an alkyl having 1 to 24 carbon atoms, an acyl having 10 to 24 carbon atoms or a substituent containing a group of the formula --(R.sub.4 O).sub.m -- wherein R.sub.4 is an alkylene group having 1 to 5 carbon atoms and m an integer of 1 to 10; ##STR3## wherein [R.sub.3 ] means plural alkyl or hydroxyalkyl groups corresponding in number to the integer 1, which may be the same or different, each having 9 to 23 carbon atoms, R.sub.4 an alkylene group having 1 to 5 carbon atoms, k an integer of 0 to 7, l an integer of 2 to 8 and Z a l-valent residue of l-valent polyhydric alcohol from which l hydroxyl groups are eliminated.
The expanded product obtained by using the composition of the present invention as mentioned above is also novel when a polyolefin resin is used as the thermoplastic resin. Thus, the present invention also provides an expanded article of a polyolefin resin, comprising an expanded product of a polyolefin resin containing at least one compound selected from the group consisting of the compounds represented by the formulas (I), (II) and (III) as mentioned above in an amount of 0.1 to 10%by weight based on said resin and having closed cellular characteristic value of 0 to 0.5 g/cm.sup.3, a bulk density of 10 to 200 kg/m.sup.3 and a compressive strength coefficient of 2.15.times.10.sup.-3 to 2.89.times.10.sup.-2.
In the accompanying drawings:
FIG. 1 shows the relationship of the volume change (ordinate) of the expanded product of the present invention (obtained in Experiment I) with lapse of time (abscissa) in which the marks , , .DELTA., and .cndot. correspond to Sample No. 1 to No. 5, respectively;
FIG. 2 compressive strength (at 25% compression) of several expanded products of polyethylene resin containing the additives according to the present invention and of polyethylene containing no additive plotted as ordinate versus bulk density of said products as abscissa;
FIG. 3 compressive strength (at 25% compression) of several expanded products of ethylene-vinyl acetate copolymer resin containing the additive and also of the same resin containing no additive plotted as ordinate versus bulk density of said products as abscissa (In FIG. 2 and FIG. 3 the two straight lines in the drawings correspond to critical values 2.15.times.10.sup.-3 and 2.89.times.10.sup.-2, respectively);
FIG. 4 the change in volume percentage (ordinate) of expanded products (obtained in Example 10 and Comparison example 1) based on the volumes immediately after expansion with lapse of time (abscissa); and
FIG. 5 the change in weight percentage (ordinate) of expanded products (obtained in Example 10 and Comparison example 1) based on the weight immediately after expansion with lapse of time. (In FIG. 4 and FIG. 5 the marks and .cndot. correspond to Example 10 and Comparison example 1, respectively).
The specific feature of the present invention resides in use of at least one compound selected from the three classes of the compounds (I), (II) and (III) as mentioned above.
The first class of the compounds are higher alkyl amines and N-substituted derivatives thereof as represented by the above specified formula (I). The alkyl group represented by R.sub.1 is required to have 10 to 24 carbon atoms, preferably 12 to 22 carbon atoms. It may either be straight chain, branched or alicyclic. But for the practical reason from economical standpoint such as commercial availability or cost, a straight chain alkyl having 12 to 22 carbon atoms may preferably be used. The alkyl amines (I) to be used in the present invention are inclusive of primary, secondary and tertiary amines. Thus, both of X and X' may be hydrogen atom, or one or both of them may be substituents.
Preferable examples of substituents are as follows:
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(a) an alkyl having 1 to 24 carbon atoms
(b) (CH.sub.2).sub.nNH.sub.2 (n is an integer of 1 to 22)
(c)
##STR4##
(d) (R.sub.4 O) .sub.mH
(e)
##STR5##
(f)
##STR6##
(g)
##STR7##
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As preferable combinations of X and X', when one of X and X' is the group (a), the other is the group (b) or (c); when one of X and X' is hydrogen atom or the group (d) or (e), the other is hydrogen atom or any of the groups (a) to (g).
Typical examples of the compounds according to the formula (I) may include dodecyl amine, tetradecyl amine, hexadecyl amine, octadecyl amine, eicosyl amine, docosyl amine, N-methyl dodecyl amine, N-methyl octadecyl amine, N-ethyl octadecyl amine, dodecyl propylene diamine, tetradecyl propylene diamine, hexadecyl propylene diamine, octadecyl propylene diamine. N-methyl hexadecyl propylene diamine, N,N'-dimethyl hexadecyl propylene diamine, N-methyl octadecyl propylene diamine, N,N'-dimethyl octadecyl propylene diamine, hexadecyl ethylene diamine, octadecyl ethylene diamine, N-methyl hexadecyl ethylene diamine, N-methyl octadecyl ethylene diamine, and the like. Typical examples of the saturated higher aliphatic amine derivatives are polyoxyethyiene myristyl amine, polyoxyethylene palmityl amine, polyoxyethylene stearyl amine, polyoxypropylene palmityl amine, polyoxypropylene stearyl amine, miristyl amine acetate, palmityl amine acetate, stearyl amine acetate, polyoxyethylene lauryl amine mono(and di-)palmitate, polyoxyethylene lauryl amine mono(and di-)stearate, .[.and.]. polyoxyethylene palmityl amine mono(and di-)palmitate, polyoxyethylene palmityl amine mono(and di-)stearate, polyoxyethylene stearyl amine mono (and di-)palmitate, polyoxyethylene stearyl amine mono(and di-)stearate, N-methyl polyoxyethylene stearyl amine palmitate, N-ethyl polyoxyethylene stearyl amine stearate, lauryl mono (and di-)ethanolamine palmitate, lauryl mono(and di-)ethanolamine stearate, palmityl mono(and di-)ethanolamine palmitate, palmityl mono(and di-)ethanolamine stearate, stearyl mono (and di-)ethanolamine palmitate, stearyl mono(and di-)ethanolamine stearate, dodecyl propylene diamine oxyethylene addition product, hexadecyl propylene diamine oxyethylene addition product, octadecyl propylene diamine oxyethylene addition product, polyoxyethylene hexadecyl propylene diamine mono(and di-)palmitate, polyoxyethylene hexadecyl propylene diamine mono(and di-)stearate, polyoxyethylene octadecyl propylene diamine mono(and di-)palmitate, polyoxyethylene octadecyl propylene diamine mono(and di-)stearate, and the like.
The second class of the compounds are saturated fatty acid amides and derivatives thereof as represented by the formula (II) as specified above. The alkyl group R.sub.2 in the formula (II) is required to have 9 to 23 carbon atoms, preferably 11 to 21 atoms, and may be either straight chain, branched or cyclic. For the same practical reason as mentioned above in connection with R.sub.1, R.sub.2 may preferably a straight chain alkyl having 11 to 21 carbon atoms. Similarly, each of Y and Y' may either be hydrogen atom or a substituent. As substituents, there may be mentioned an alkyl having 1 to 24 carbon atoms, an acyl having 10 to 24 carbon atoms or a group of the formula --(R.sub.4 O).sub.m A.sub.2 (wherein m is an integer of 1 to 10 and A.sub.2 hydrogen atom, an alkyl having 1 to 24 carbon atoms or an acyl having 10 to 24 carbon atoms).
Typical examples of the compounds (II) are lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, arachic acid amide (eicosyl amide), behenic acid amide (docosyl amide), N-methyl stearic acid amide, N,N'-dimethyl stearic acid amide, di-lauric acid amide, di-palmitic acid amide, di-stearic acid amide, tri-lauric acid amide, tri-palmitic acid amide, tri-stearic acid amide, and so on. The saturated higher fatty acid amide derivatives may include lauric acid mono(and-di-)ethanolamide, myristic acid mono(and di-)ethanolamide, palmitic acid mono(and di-)ethanolamide, stearic acid mono(and di-)ethanolamide, arachic acid mono(and di-)ethanolamide, behenic acid mono(and di-)ethanolamide, lignoceric acid mono(and di-)ethanolamide, lauric acid mono-isopropanolamide, palmitic acid mono-isopropanolamide, stearic acid mono-isopropanolamide, polyoxyethylene lauric acid amide, polyoxyethylene myristic acid amide, polyoxyethylene palmitic acid amide, polyoxyethylene stearic acid amide, polyoxyethylene arachic acid amide, di-lauric acid mono-ethanolamide, di-myristic acid mono-ethanolamide, di-palmitic acid mono-ethanolamide, di-stearic acid mono-ethanolamide, di-arachic acid mono-ethanolamide, polyoxyethylene di-stearic acid amide, polyoxyethylene lauric acid amide.mono-stearate, polyoxyethylene stearic acid amide.mono-stearate, etc.
The third group of the compounds are complete esters of saturated higher fatty acids as represented by the formula (III) as specified above. They are complete esters of polyhydric alcohols of the formula Z(OH).sub.l and saturated fatty acids having 10 to 24 carbon atoms. In the above formula, the symbol [R.sub.3 ] means plural alkyl groups comprehensively, each being attached to each ester linkage which is bonded to polyhydric alcohol residue represented by Z, and each having 9 to 23 carbon atoms. Also in this compound, straight chain alkyl having 11 to 21 carbon atoms is preferred. The complete esters may be modified by addition reaction to include polyoxyalkylene group of the formula --(OR.sub.4).sub.k -- in the molecule. The oxyalkylene group --OR.sub.4 -- may preferably oxyethylene or oxypropylene.
Typical examples of the compounds (III) are polyoxyethylene di-myristate, polyoxypropylene di-myristate, polyoxyethylene di-palmitate, polyoxypropylene di-palmitate, polyoxyethylene di-stearate, polyoxypropylene di-stearate, polyoxyethylene di-arachate, polyoxyethylene di-behenate, ethyleneglycol di-myristate, ethyleneglycol di-palmitate, ethyleneglycol di-stearate, ethyleneglycol di-arachate, ethyleneglycol di-behenate, lauric acid tri-glyceride, myristic acid tri-glyceride, palmitic acid tri-glyceride, stearic acid tri-glyceride, arachic acid tri-glyceride, 1,3-palmito-2-stearic acid glyceride, 1,3-stearo-2-myristic acid glyceride, sorbitane tetra-palmitate, sorbitane tetra-stearate, 12-hydroxy stearic acid tri-glyceride, sorbitane tetra-12-hydroxystearate, mono-stearic acid-di-12-hydroxystearic acid tri-glyceride, polyoxyethylene glycerine tristearate, polyoxyethylene glycerine tri-12-hydroxystearate, polyoxyethylene sorbitane tetra-stearate, polyoxyethylene sorbitane tetra-12-hydroxystearate, monostearic acid-di-12-hydroxy stearic acid polyoxyethylene tri-glyceride, and the like.
It is critically required in the present invention that at least one compound selected from the group of the compounds (I), (II) and (III) as described above should be contained in the thermoplastic synthetic resin in a total amount of 0.1 to 10% by weight based on the weight of said resin.
Referring now to Experiments I to IV set forth below, the specific behavior of the compounds within the scope of the present invention when they are contained in an amount within the range as specified above is to be described.
EXPERIMENT IUsing an ethylene-vinyl acetate copolymer (EVATATE D-2021, trade mark, produced by Sumitomo Chemical Co., Ltd.; vinyl acetate content: 10 wt. %, density: 0.93, Melt Flow Index: 1.5) as base resin, various samples are prepared by adding the compounds as shown in Table 1 and each sample is fabricated into a non-stretched sheet with thickness of about 0.15 mm.
TABLE 1
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Additives
Parts per
100 parts
Sample Principal of resin
No. Trade name component (by weight)
Manufacturer
______________________________________
1 Amine A . B
Octadecyl 2 Nippon Oils &
amine Fats Co., Ltd.
2 Fatty acid Stearic 2 Kao Soap
amide T acid amide/ Co., Ltd.
palmitic
acid amide
3 Hardened Stearic 5 Kao Soap
oil acid tri- Co., Ltd.
glyceride
4 Span 85 Sorbitane 2 Kao Soap
(reference)
tri-oleate Co., Ltd.
5 -- (Control)
-- -- --
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The gas permeability characteristics of these sheets are measured according to the following method:
Device: Gas-permeability measuring instrument (LYSSY-L100-3001 model, produced by LYSSY Co.)
Gases to be permeated: Air; Dichlorotetrafluoroethane (blowing agent)
Method: Gas permeability coefficient is determined by measuring the time (seconds) needed until the inner pressure of a vessel initially maintained at 0.2 Torr at about 30.degree. C. is increased to 0.4 Torr by the gas permeated through the sample sheet. The time is measured repeatedly until its value becomes approximately constant, and the average value of three measured values is divided by the thickness of the sheet to give the gas permeability coefficient.
The results of measurement are given in the following Table 2
TABLE 2
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Sample No
1 2 3 4 5
Additive
Fatty
acid Har-
Permeated
Amine amide dened Span 85
gas AB T oil (reference)
Control
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1,2-dichloro-
244 255 320 121 79
fluoro ethane
Air 340 350 380 490 320
units sec/mm
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As apparently seen from Table 2, the compositions according to the present invention (Sample Nos. 1, 2 and 3) suppress noticeably permeability of blowing agent gas as compared with Control (Sample No. 5), while they suppress little permeability of the air. On the contrary, the composition of the reference (Sample No. 4) slightly suppresses permeability of the blowing agent gas, while it greatly suppresses permeability of the air.
Based on the presumption that the well-balanced permeabilities of the air and the blowing agent gas through the resin compositions of the present invention as shown in Table 2 might be reflected in expansion procedure to result in ideal expanded products, the present inventors have made experiments to apply these compositions for manufacturing expanded products of polyethylene and ethylene-vinyl acetate copolymer resin in spite of the fact that expansion molding of polyethylene resin under uncrosslinked state has been deemed to be difficult and also that expansion molding with high closed cell percentage of ethylene-vinyl acetate copolymer resin has been substantially impossible.
The following Experiments II-IV illustrates the results of these experiments.
EXPERIMENT IIEach of the resin compositions according to Sample Nos. 1 to 5 as described in Experiment 1 is mixed with 0.1 part by weight of calcium stearate and 0.6 part by weight of calcium stearate and fed to an extruder (30 mm.PHI.). The mixture is kneaded internally of the extruder together with 28 parts by weight of 1,2-dichlorotetrafluoroethane and the thus mixed resin is extruded into the air while being maintained at about 90.degree. C. to effect expansion to obtain expanded products. The density of the expanded products obtained is controlled to be 36 to 37 kg/m.sup.3.
The volume of the resultant expanded product is thereafter continued to be measured day by day. On the other hand, for the expanded product after 10 days, there are conducted measurements of compressive strength, compression permanent set, compression creep, surface smoothness, maximum shrinkage of the expanded product after expansion, dimensional stability of the expanded product and closed cellular characteristic value (each measurement method is hereinafter described).
FIG. 1 shows the relationship of the volume change with lapse of time and Table 3 the results of the measurement of various characteristics for each expanded product.
The compressive strength coefficient is also determined from the formula (2) as hereinafter described and shown in Table 3 in bracket together with 25% compressive strength (according to JIS-K-6767), since the latter varies depending on the density of the expanded product, etc.
As is clear from the above results, the composition of the present invention can be expanded using a blowing agent to give feasibly expanded products with good quality of uncrosslinked polyethylene which has hitherto been deemed to be difficult in the prior art as well as expanded products with good quality of ethylene-vinyl acetate copolymer resin which cannot practically be prepared in the prior art.
TABLE 3
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Characteristics of expanded products
(measured after 10 days after expansion)
Evaluation Items
Density Maximum
[kg/m.sup.3 ] Compressive
Permanent foam shrink- Closed
Items
Immediate-
After
strength
set at 50%
Compres-
Surface
age after
Dimensional
cellular
Sample
ly after
10 kg/cm.sup.2
compression
sive creep
smoothness
expansion
stability
characteristic
No. expansion
days
(coefficient)
(%) (%) (number/cm)
(Vol. %)
of foam
value
__________________________________________________________________________
(g/cm.sup.3)
1 36 34 1.48 10 6 0 8.0 3 0.0008
(2.82 .times. 10.sup.-2)
2 36 34 1.46 11 6 0 5.5 5 0.0012
(2.80 .times. 10.sup.-2)
3 36 34 1.47 11 6 0 7.5 7 0.0024
(2.81 .times. 10.sup.-2)
4 37 64 0.10 28 24 14 51 8 0.0135
(9.3 .times. 10.sup.-4)
5 37 51 0.11 24 21 12 35 19 0.0114
(1.35 .times. 10.sup.-3)
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The concept of compressive strength coefficient is herein introduced to specify the novel expanded articles obtained by use of the composition according to the present invention. This is because apparent compressive strength as shown in Table 3 varies depending on bulk density of the expanded product and therefore it is not desirable to characterize the expanded product in terms of such an apparent compressive strength. As the result of numerous experiments, the present inventors were successful in generalization of the compressive strength relative to bulk, density according to the following formula:
P=A.times.D.sup.1.248.Y
From the formula (1) is obtained:
A=P/D.sup.1.248.Y
wherein A represents compressive strength coefficient, P 25% compressive strength measured according to JIS-K-6767, D bulk density of expanded product, the value 1.248 is the index experimentally determined from numerous data, Y is parameter (1-.alpha./100), .alpha. being percentage (wt.) of the component to be copolymerized in the resin (for example, vinyl acetate in ethylene-vinyl acetate copolymer). This specific compressive strength coefficient is hereinafter referred to as "A value".
EXPERIMENT IIIUsing a low density polyethylene (Asahi-Dow Polyethylene F-1920, trade mark, produced by Asahi-Dow Limited; density: 0.919, Melt Flow Index 2.0) as base resin, the compositions 1 to 11 containing the additives and blowing agents as shown in Table 4, respectively, per 100 parts by weight of said resin are prepared by kneading similarly in an extruder and subjected to extrusion expansion as in Experiment II. As nucleators, there are employed 0.06 parts by weight of calcium stearate and 0.36 parts by weight of calcium silicate in each composition. After 10 days after formation of expanded product, 25% compressive strength is measured according to JIS-K-6767 for each expanded product from each composition to give the results as shown in FIG. 2, the numbers in FIG. 2 corresponding to those of the compositions.
EXPERIMENT IVUsing an ethylene-vinyl acetate copolymer (EVATATE K-2010, trade mark, produced by Sumitomo Chemical Co., Ltd.; vinyl acetate content 25 wt. %, density: 0.95, Melt Flow Index: 3.0) as base resin, 0.1 part of calcium stearate and 0.6 part by weight of calcium silicate as nucleators and the additives and blowing agents as shown in Table 5, under otherwise the same conditions as in Experiment III, the compositions 12 to 20 are formed into expanded products. The results of measurement conducted similarly as in Experiment III are shown in FIG. 3, wherein the numbers correspond to those of the compositions.
TABLE 4
______________________________________
Com-
po-
sition
No. Blowing agent (wt parts)
Additive (wt parts)
______________________________________
1 Dichlorodifluoromethane (57)
Fatty acid amide T (4.0)
2 Dichlorodifluoromethane (57)
None
3 Dichlorodifluoromethane (22)
Fatty acid amide T (2.0)
4 Dichlorodifluoromethane (22)
None
5 Dichlorodifluoromethane (5)
Amine AB (1.0)
6 Butane(8) Hardened oil (3.0)
7 Butane(8) None
8 Butane(6) Fatty acid amide T (0.5)
9 Butane(6) None
10 1-chloro-1,1difluoro-
Hardened oil (2.0)
ethane (60)
11 1-chloro-1,1-difluoro-
None
ethane (60)
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TABLE 5
______________________________________
Com-
po-
sition
No. Blowing agent (wt parts)
Additive (wt parts)
______________________________________
12 1,2-dichloro-tetrafluoro
Amine AB (1.0)
ethane (10)
13 Dichlorodifluoromethane (57)
Fatty acid amide T (5.0)
14 Dichlorodifluoromethane (57)
None
15 Dichlorodifluoromethane (22)
Fatty acid amide T (4.0)
16 Dichlorodifluoromethane (22)
None
17 Butane (7) Hardened oil (2.0)
18 Butane (7) None
19 1-chloro-1,1-difluoro-
Hardened oil (3.0)
ethane (60)
20 1-chloro-1,1-difluoro-
None
ethane (60)
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As apparently seen from FIG. 2 and FIG. 3, the A values of the expanded products obtained by use of the compositions of the present invention are invariably within 2.15.times.10.sup.-3 to 2.89.times.10.sup.-2 even when the blowing agent employed may be varied. In contrast, the A values of the expanded products using no composition of the present invention are by far smaller than the range as specified above. While being not bound by any theory, this is probably due to the following reason. Blowing agent gases contained in the expanded products are rapidly dissipated therefrom at the stage immediately after expansion in case when no composition of the present invention is employed, while the air penetrates into the expanded product considerably slowly. Consequently, at the stage before complete solidification of the resin while it is hot, the expanded product is brought internally to a state under reduced pressure, whereby it is compressed by atmospheric pressure to be shrinked. Thus, cooling is completed while giving deformations or cracks on cell walls. When the penetration of the air is slower than the cooling speed as mentioned above, the expanded product is cooled as it is to result in an expanded product with high density and having a large number of permanent creases remained on the expanded product. Even when the air may be penetrated more rapdily, simultaneously with reduction in pressure in the expanded product, to effect surface expansion of the expanded product, the deformations or cracks already formed on cell walls will prevent such surface expansion to make restoration to original volume difficult. This speculation is considered to be quite probable because the A values of the expanded products are greatly deteriorated.
Whereas, in the expanded product prepared from the composition of the present invention, the resin can be solidified with very small extent of shrinkage by permitting blowing agent gases to be replaced by the air while maintaining the ratio of both gases permeated suitably. As the result, the expanded product can be free from deformations or cracks on the cell walls to exhibit not only the excellent compressive strength coefficient but also excellent surface smoothness.
If the specific compound of the present invention is used in less than 0.1 wt. % based on the resin, no significant effect can be otained. On the contrary, an amount in excess of 10 wt. % does not necessarily lead to improvement of the effect but in some cases may cause an adverse effect on the rheological flow properties of the composition itself. Accordingly, the amount of the specific compound added is generally selected from about 0.5 to 7 wt. % from economical standpoint. There is no significant change in the amount of the compound added when it is in the composition or when it is in the expanded product, and it is calculated as a total amount of the specific compounds employed based on the weight of the resin.
For the purpose of the invention, there may be employed either a single compound or a combination of two or more compounds selected from those as mentioned above. The compound may be incorporated in the resin by any method but it is desirable to contain the compound in the resin so that said compound may be dispersed as homogeneously as possible in the resin when the composition is formed into an expanded product.
In accordance with the present invention, there is also provided a process for expanding a thermoplastic synthetic resin, which comprises incorporating at least one compound selected from the group consisting of the compounds of the formulas (I), (II) and (III) as described above in the thermoplastic synthetic resin in an amount of 0.1 to 10% by weight based on said resin together with a suitable amount of a blowing agent under the condition maintained at a temperature in the range from about 15.degree. to 300.degree. C. to form an expandable resin composition and then allowing said resin composition to expand utilizing the expanding force of the blowing agent contained therein.
In the process as specified above, the compounds may be incorporated in the resin by so called impregnation method wherein a substance to be incorporated is contacted with resin particles and said substance is impregnated into the resin by controlling the pressure and the temperature. Alternatively, there may also be employed so called kneading method wherein the resin and the substance to be incorporated are subjected to mixing and kneading. Furthermore, a combination of both methods may also be applicable. The substances to be incorporated may either be simultaneous or stepwise. These operations may be conducted under well known conditions, namely at a temperature in the range from 15.degree. to 300.degree. C. and a pressure of 0.05 to 300 kg/cm.sup.2 (gauge).
The expanding force of blowing agent used in this process is obtained through phase transfer (from liquid phase to gas phase), volume expansion of blowing agent and decomposition of blowing agent (from solid to gas), and therefore the conditions are determined depending on the blowing agent employed and expanding operations. For example, when a physical blowing agent is used in extrusion expansion, a resin kneaded for temperature adjustment at a temperature of about 60.degree. to 280.degree. C. under a pressure of 5 to 200 kg/cm.sup.2 can be extruded into the atmosphere at a temperature of about 20.degree. C. and under pressure of 1 atm. to obtain sufficient expanding force. Alternatively, when a physical blowing agent is used in cavity expansion, a resin containing a blowing agent is filled in a cavity and the cavity is heated under conditions at a temperature of about 115.degree. C. under pressure of 0.23 kg/cm.sup.2 (gauge).
The specific feature of the process according to the present invention resides in allowing a thermoplastic synthetic resin composition containing 0.1 to 10 wt. % of at least one compound as specified by the formulas (I), (II) and (III) to expand with a blowing agent which is also contained in said resin. This is because, in the absence of the specific compound, the expanded product suffers from shrinkage in the course of preparation and with lapse of time, as explained with reference to FIGS. 1 to 3 and Table 3, thereby giving only expanded products with high density, having much concavo-convex deformations or creases or being very low in closed cell percentage. In particular, no expanded product with excellent compressive strength can be obtained in the absence of the specific compound.
Similarly as described in connection with the composition of the present invention, an amount of the specific compound less than 0.1 wt. % fails to give the effect of the invention, while an amount exceeding 10 wt. % may cause adverse effect rather than better results. The specific compounds may also be used either singly or in a mixture of two or more compounds. The preferable total amount of the specific compounds falls also within 0.5 to 7 wt. %. They can be contained in the resin in any conventional manner, but it is desirable to disperse the compounds as homogeneously as possible throughout the entire resin.
As blowing agents to be used in the present invention, volatile organic blowing agents and thermally decomposable gas-releasing chemical blowing agents are available. Preferably, there may be employed volatile organic blowing agents having boiling point (at 1 atm.) not higher than melting point of the base resin, such as trichlorofluoromethane, dichlorodifluoromethane, dichlorofluoromethane, chlorodifluoromethane, 1,1',2-trichlorotrifluoroethane, 1,2-dichlorotetrafluoroethane, 1-chlorotrifluoroethane, 1-chloro-1,1'-difluoroethane, 1,1'-difluoroethane, octafluorodichlorobutane, propane, butane, butene, propylene, pentane, etc. When the base resin to be expanded is a non-crosslinked polyolefin resin, it is preferred to select a volatile blowing agent from those as enumerated above having a Kauri-Butanol value in the range of 10 to 25 as determined by the method according to ASTM-D-1133-61.
These blowing agents may be employed generally in an amount in the range from 5 to 70% by weight based on the resin depending on the desired density of expanded products.
The process of the present invention is expected to be most advantageously be applied in the field of so called continuous extrusion expansion. In this case, for example, the base resin, the specific compound and blowing agent are fed into an extruder heated at a temperature higher than melting point of the base resin (generally about 120.degree. to 280.degree. C.), kneaded under a pressure generally of about 50 to 300 kg/cm.sup.2 therein, then said mixture is adjusted to a temperature suitable for expansion in the range from the melting point of the base resin to the temperature lower by 50.degree. C. than the melting point (generally about 60.degree. to 200.degree. C.) before being extruded through an orifice to the outside at about 25.degree. C. under atmospheric pressure, thereby accomplishing expansion simultaneously with extrusion, followed by cooling to produce expanded articles. This technique is economical in continuous expansion of a large amount of resins. In particular, by use of the specific compound of the present invention, it is rendered possible to select a blowing agent from a large number of less expensive compounds which have hitherto been insufficient in expandability when used alone as blowing agents. To speak one typical example, in place of an expensive blowing agent 1,2-dichlorotetrafluoroethane, there can be employed less expensive blowing agents such as dichlorodifluoromethane, propane or butane to a great economical advantage.
The thermoplastic synthetic resin to be used in the present invention refer to all polymers, copolymers and mixed polymers which can be subjected to melt fabrication. In particular, thermoplastic synthetic resins which can be improved in expandability by addition of the specific compound of the present invention are those which will undergo shrinkage when expanded due to the greater ratio S'/S exceeding 1 of permeating speed (S') of volatile hydrocarbon or fluorocarbon gas through said resin film to that (S) of the air (at the time of expansion as estimated by FIG. 4 and FIG. 5). More specifically, they may include crosslinked or non-crosslinked polyolefin resins such as ethylene homopolymers (e.g. high density polyethylene, medium density polyethylene or low density polyethylene or a mixture thereof), ethylenic copolymers having ethylene content of 50% or more (e.g. ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer, a metallic salt of an ethylene-acrylic acid copolymer, ethylene-propylene copolymer, ethylene-vinyl chloride copolymer), polypropylene and polybutene-1. Among them, polyethylene resin and ethylene-vinyl acetate copolymer are preferably used. The polyolefin resin to be employed in the present invention may have a melt index which is not specifically limited but generally within the range from 0.3 to 45. When it is desired to employ a crosslinked polyolefin resin, it may be prepared by conventional method by effecting crosslinking using a crosslinking agent such as organic peroxides or irradiation of electron beam.
The resin composition of the present invention may further contain, if desired, other inorganic or organic additives such as pigments, fire-retardants, lubricants, anti-oxidants, UV-absorbers, nucleators, anti-static agents or others in an amount of preferably no more than 3% by weight based on the weight of the resin. In particular, it is preferable to use a small amount (not more than 1% by weight) of nucleators such as talc or a fatty acid metal salt in order to control uniformly the cell distribution in the resultant expanded product.
The present invention is further illustrated with reference to the following Examples and Comparison Examples. The measurement of characteristic values and evaluation of these values herein mentioned are conducted by the methods and the criteria, respectively, as set forth below.
1. Compressive strength and compressive strength coefficient
(a) 25% compressive strength (P):
Compressive strength at the time of 25% compression is measured according to JIS-K=6767.
(b) compressive strength coefficient (A):
This value is calculated by the formula (2) as mentioned above from the above compressive strength (P) and bulk density (D) of expanded product.
2. 50% compression permanent set:
According to JIS-K-6767 (at the time of 50% compression).
3. Compression creep:
According to JIS-K-6767 (under area load of 0.1 Kg/cm.sup.2 .multidot.24 hour)
4. Surface smoothness:
The surface of expanded product is measured over 10 cm length by coarseness measuring instrument to detect creases or concavo-convexes with width of 0.5 mm or more and the number detected is calculated per 1 cm length.
5. Feeding characteristic through extruder:
Change in amount extruded per one minute when performing extrusion by 30 mm.PHI. extruder is expressed by variance percentage (n=15). ##EQU1## 6. Maximum shrinkage: Volume of expanded product is masured (by watersink method) every day for 20 days after expansion and maximum shrinkage is calculated by the following formula: ##EQU2## 7. Dimensional stability: From the result of measurement 6. as mentioned above, dimensional stability is calculated by the following formula: ##EQU3## (wherein V.sub.0 is volume of expanded product immediately after expansion and V.sub.20 that after 20 days.)
8. Closed cellular characteristic value:
In water in a vessel having water volume sufficient to sink sample in water and a function to be sealed is sunk an expanded product sample of 15 mm.times.15 mm.times.100 mm (volume: V; weight: W.sub.0) to be held therein, followed by sealing of the vessel. Subsequently, the inner pressure in the vessel is reduced to 460 mm Hg and left to stand for 10 minutes. Then, the inner pressure in the vessel is restored to atmospheric and the sample is taken out. The sample is calmly dipped in pure methanol for about 2 seconds, followed by wipe-off of the moisture adhered on the surface, dried in a drier at 60.degree. C. for 5 minutes and thereafter its weight (W.sub.1) is measured. Closed cellular characteristic value is calculated by the following formula: ##EQU4## 9. Criteria for evaluation: Each evaluation item is rated according to the ranks as shown in the following Table:
______________________________________
Ranks
Evaluation a b c d
item (excellent)
(good) (passable)
(bad)
______________________________________
1. Compressive
8.0 .times. 10.sup.-3
4.0 .times. 10.sup.-3
2.15.times. 10.sup.-3
less
strength or more or more,
or more,
than
coefficient less than
less than
2.15 .times.
8.0 .times. 10.sup.-3
4.0 .times. 10.sup.-3
10.sup.-3
2. 50% less than 5 or more
15 or more
30 or
compression
5 to 0 less than 15
less than 30
more
permanent
wt (%)
3. Compressive
less than 5 or more,
10 or more,
20 or
creep (%) 5 to 0 less than 10
less than 20
more
4. Surface less than 3 or more,
6 or more,
10 or
smoothness 3 to 0 less than 6
less than 10
more
(number/cm)
5. Feeding less than 5 or more,
10 or more,
15 or
character- 5 to 0 less than 10
less than 15
more
istic of
extruder (%)
6. Maximum less than 10 or more,
15 or more,
20 or
shrinkage 10 to 0 less than 15
less than 20
more
(%)
7. Dimensional
less than 5 or more,
10 or more,
15 or
stability 5 to 0 less than 10
less than 15
more
(%)
8. Closed less than 0.010 or
0.025 or
0.50 or
cellular 0010 to 0 more, less
more, less
more
characteristic than 0.025
than 0.50
(g/cm.sup.3)
______________________________________
Overall evaluation is rated from the ranks as set forth above according to the following ranks:
______________________________________
a (excellent)
when there are at least two excellent
marks with no bad or passable mark
b (good) when there is at least one good mark
with no bad mark and not more than
two passable marks
c (passable) when there are three or more passable
marks with no bad mark
d (bad) when there is one or more bad mark
______________________________________
The details of the thermoplastic synthetic resins and the specific compounds employed in the following Examples and Comparison Examples are listed below.
Thermoplastic resins:
Resin A: low density polyethylene produced by Asahi-Dow Limited, F-1920, trade mark, density: 0.919 g/cc, MI: 2.0 g/10 min.
Resin B: ethylene-vinyl acetate copolymer produced by Sumitomo Chemical Co., Ltd., EVATATE D-2021, trade mark, vinyl acetate content: 10 wt. %, density: 0.93 g/cc, MI: 1.5 g/10 min.
Resin C: ethylene-vinyl acetate copolymer produced by Sumitomo Chemical Co., Ltd., EVATATE K-2010, trade mark, vinyl acetate content: 25 wt. %, density: 0.95 g/cc, MI: 3.0 g/10 min.
Additives (Nos. 1-18: specific compounds of the invention; Nos. 19-31: reference compounds)
______________________________________
Trade name of Name of
No. additives Manufacturer
the compounds
______________________________________
1 Fatty acid Kao Soap Co.,
Stearic acid amide and
amide T Ltd. palmitic acid amide
(mixture)
2 Amine BB Nippon Oils &
Dodecyl amine
Fats Co., Ltd.
3 Amine AB Nippon Oils &
Octadecyl amine
Fats Co. Ltd.
4 N--methyl- Nippon Oils &
N--methyloctadecyl
octadecyl Fats Co., Ltd.
amine
amine
5 Asfazol #20 Nippon Oils &
Stearyl propylene
Fats Co., Ltd.
diamine
6 Naimine S-202
Kao Soap Co.,
Polyoxyethylene octa-
Ltd. decyl amine (2 moles
of oxyethylene added)
7 Naimine S-210
Kao Soap Co.,
Polyoxyethylene octa-
Ltd. decyl amine (10 moles
of oxyethylene added)
8 Denon 331 P Marubishi Polyoxyethylene stearyl
Petrochemical
amine mono- and di-
Co. stearate (mixture)
9 Esodaomine Lion Fat & Polyoxyethylene stearyl
T-13 Oil Co., Ltd.
and palmityl diamine
(mixture: 3 moles of
oxyethylene added)
10 Resicoat 1936
Lion Fat & Oxyethylene stearyl and
Oil Co., Ltd.
palmoctyl diamine
(mixture: one mole of
oxyethylene added)
11 Fatty acid Kao Soap Co.,
Lauric acid amide
amide C Ltd.
12 Amazol SDE Kawaken Fine
1:1-type stearic acid
Chemical Co.,
dictbanolamide
Ltd.
13 Amazol SME Kawaken Fine
1:1-type stearic acid
Chemical Co.,
mono-ethanolamide
Ltd.
14 Amozol LME Kawaken Fine
1:1-lauric acid
Chemical Co.,
mono-ethanolamide
Ltd.
15 Fatty acid Kao Soap Co.,
Palmitic acid amide
amide P Ltd.
16 Hardened oil
Kao Soap Co.,
Stearic acid triglyceride
Ltd.
17 Koa wax 85 Koa Soap Co.,
12-hydroxy stearic acid
powder Ltd. triglyceride
18 Unister-E-275
Nippon Oils &
Ethyleneglycol
Fats Co., Ltd.
distearate
19 Syntolex Nippon Oils &
Sodium lauryl sulfate
L-100 Fats Co., Ltd.
20 A.mos-150 Kao Soap Co.,
Stearic acid mono- and
Ltd. di-glyceride
21 Cation Nippon Oils &
Octadecyl dimethyl-
S.sub.2 -100
Fats Co., Ltd.
benzyl ammonium
chloride
22 Noion Nippon Oils &
Polyoxyethylene
SN-204.5 Fats Co., Ltd.
nonyl phenol ether
23 Caproic Kanto Chemical
Caproic acid amide
acid amide Co., Ltd.
24 Span 85 Kao Soap Co.,
Sorbitane trioleate
Ltd.
25 Triphenyl Kanto Chemical
Triphenyl carbinol
carbinol Co., Ltd.
26 1,2-diphenyl
Kanto Chemical
1,2-diphenyl ethylene-
ethylene- Co., Ltd. diamine
diamine
27 Phthalamide Kanto Chemical
Phthalamide
Co., Ltd.
28 Lunac S-30 Kao Soap Co.,
Stearic acid
Ltd.
29 Zinc stearate
Sakai Zinc stearate
Chemical Co.,
Ltd.
30 Fatty acid Kao Soap Co.,
Oleic acid amide
amide O Ltd.
31 Alfro P-10 Nippon Oils &
Erucic amide
Fats Co., Ltd,
______________________________________
EXAMPLES 1-18 AND COMPARISON EXAMPLES 1-14
To 100 parts by weight of Resin B are added various additives as shown in Table 6, 0.1 part by weight of calcium stearate, 0.6 part by weight of calcium silicate and 22 parts by weight of a volatile blowing agent dichlorodifluormethane. Each mixture is kneaded by means of a 30 mm single screw extruder equipped with a round orifice of 5 mm in diameter and heated at 190.degree. C. By adjusting the resin temperature in the orifice at 90.degree. C., extrusion expansion is carried out for each mixture to prepare an expanded product thereof. These expanded products are subjected to evaluation test as described above to give the results as shown in Table 6. Table 6 clearly shows that the expanded products of Examples 1 to 18 containing the compounds of the formulas (I) to (III) exhibit superior values to those of Comparison example 1 containing no additive and Comparison examples 2 to 14 containing other compounds than those of the formulas (I) to (III).
The volumes and weights of the expanded products obtained in Example 10 and Comparison example 1 are continued to be measured every day for about one month, respectively, and the percentages of volumes and the weights based on those immediately after expansion are plotted versus lapse of time (days) in FIG. 4 and FIG. 5.
As apparently seen from FIG. 4 and FIG. 5, the expanded product of Example 10 is reduced in weight with lapse of time, while its volume is not reduced with small shrinkage and good restorability. In contrast, the expanded product of Comparison example 1 suffers from abrupt and noticeable shrinkage with reduction in weight and its volume restored with lapse of time is at most about 60%.
3 TABLE 6
Base resin: B, 100 wt. parts Nucleators: Calcium stearate 0.1 wt.
part, calcium silicate 0.6 wt. part Blowing agent: Dichlorodifluoromethan
e 22 wt. parts .Iadd.Evaluation.Iaddend. Density Feeding Closed
(10 days after Compressive 50% characteristic Dimensional cellular
expansion) strength compression Compression Surface through Maximum
.[.stabiity.]. characteristic Overall g/cm.sup.3 coefficient permanent
set creep smoothness extruder shrinkage stability value evaluation
Additives wt. parts Type of Example compounds Trade name
1 Amine BB (2.0) 0.029 a b b a a a a a a 2 Amine AB (2.0) " a b b a a
a a a a 3 Saturated N--methyl- 0.030 a b b a a a a a a higher octadecyl
aliphatic amine (2.0) 4 amine Asfazol #20 " a b b a b a a a a compounds
(2.0) 5 Naimine S-202 0.029 a b b b b b a a a (2.0) 6 Naimine S-210
" a b b b b b a a a (2.0) 7 Denon 331P 0.030 a b b b b b a a a
(5.0) 8 Esoduomine F13 " a b b a b a a a a (3.0) 9 Resicoat 1936 " a
b b a b a a a a (3.0) 10 Fatty acid 0.029 a b b a a a a a a amide T
(1.0) 11 Saturated Fatty acid " a b b a a a a a a higher amide C (3.0)
12 fatty Amizol SDE " a b b a a a a a a acid (2.0) 13 amides Amizol SME
0.030 a b b a a a a a a (2.0) 14 Amizol LME " a b b a a a a a a
(2.0) 15 Fatty acid 0.029 a b b a a a a a a amide P (2.0) 16 Complete
Hardened " a b b a b a a a a esters oil (1.5) 17 of " a b b a b a a a
a saturated Kao wax 85 higher powder (1.5) 18 fatty Unister E275 0.030
a b b b b b a a a acids (1.5)
Comparison Additive example trade name (wt. parts) 1 None
0.075 d d d d a d d b d 2 Atmos 150 (1.5) " c c c d d c d b d 3 Syntolex
L-100 (2.0) " d d d d b d d b d 4 Cation S.sub.2 -100 (2.0) 0.073 d d d
d b d d b d 5 Nonion NS 204.5 (2.0) 0.072 d d d d d d d b d 6 Capronamide
(2.0) " d d d d a d d b d 7 Fatty acid amide O (2.0) 0.074 d d d d b d
d b d 8 Alfro P-10 (2.0) 0.074 d d d d b d d b d 9 Span 85 (2.0) " d d d
d d d d b 10 Triphenyl carbinoyl (2.0) " d d d d b d d b d 11 1,2-Dipheny
l 0.073 d d d d b d d b d ethylenediamine (2.0) 12 Phthalamide (2.0)
0.075 d d d d b d d b d 13 Lunac 5-30 (2.0) " d d d d b d d b d 14 Zinc
stearate 2.0 " d d d d b d d b d
EXAMPLES .Badd.19-27 AND COMPARISON EXAMPLES 15-17
Expanded products are prepared similarly as described in Examples 1-18 except that 100 parts by weight of Resin A are used as base resin, 0.06 parts by weight of calcium stearate and 0.36 part by weight of calcium silicate powders as nucleators and the blowing agents D, E and F as shown in Table 7 in amounts of 22, 20 and 8 parts by weight, respectively, and that the resin temperature in the orifice is controlled at 104.degree. C. From the results shown in Table 7, it is clearly seen that Examples 19 to 27 give better results than Comparison Examples 15 to 17 when various blowing agents D, E and F are employed.
TABLE 7
__________________________________________________________________________
Base resin:
A 100 wt. parts
Nucleators:
Calcium stearate 0.06 wt. parts, calcium silicate 0.36
wt. parts
Blowing agents:
D: Dichlorodifluoromethane
22 wt. parts
E: 1-chloro-1,1-difluoroethane
20 wt. parts
F: Butane 8 wt. parts
__________________________________________________________________________
Density
Evaluation
(10 days after
Compressive
50%
Blowing
expansion
strength
compression
Compression
Surface
agent
g/cm.sup.3
coefficient
permanent set
creep smoothness
__________________________________________________________________________
Additive (wt. parts)
Type of
Example compounds
Trade name
19 Saturated
Amine AB (1.0)
D 0.030 a a a a
20 higher Amine AB (3.0)
E 0.032 a b b b
21 aliphatic
Amine AB (7.0)
F 0.034 a b b b
amines
22 Saturated
Fatty acid
D 0.030 a a a a
higher amide T (0.3)
23 fatty Fatty acid
E 0.032 a b a a
acid amide T (2.0)
24 amides Fatty acid
F 0.033 a b b b
amide T (5.0)
25 Complete
Hardened D 0.030 a a a a
esters of
oil (4.0)
26 saturated
Hardened E 0.033 a b b b
higher oil (6.0)
27 fatty Hardened F 0.034 a b b b
acids oil (10.0)
__________________________________________________________________________
Comparison
example Additives
15 None D 0.063 d d d d
16 None E 0.062 d d d d
17 None F 0.069 d d d d
__________________________________________________________________________
Evaluation
Feeding Closed
characteristic cellular
through
Maximum
Dimensional
characteristic
Overall
extruder
shrinkage
stability
value evaluation
__________________________________________________________________________
Additives (wt. parts)
Type of
Example compounds
Trade name
19 Saturated
Amine AB (1.0)
a a a a a
20 higher Amine AB (3.0)
a b a a a
21 aliphatic
Amine AB (2.0)
b b a a a
amines
22 Saturated
Fatty acid
a a a a a
higher amide T (0.3)
23 fatty Fatty acid
a b a a a
acid amide T (2.0)
24 amides Fatty acid
b b a a a
amide T (5.0)
25 Complete
Hardened b a a a a
esters of
oil (4.0)
26 saturated
Hardened b b a a a
higher oil (6.0)
27 fatty Hardened b b a a a
acids oil (10.0)
__________________________________________________________________________
Comparison
example Additives
15 None a d d b d
16 None a d d b d
17 None a d d b d
__________________________________________________________________________
EXAMPLES 28-36 AND COMPARISON EXAMPLES 18-21
Using 100 parts by weight of Resin C as base resin, blowing agents D, E, G and H as shown in Table 8 in amounts of 22, 20, 28 and 26 parts by weight, respectively, and the additives as shown in Table 8 in amounts indicated therein, and also adjusting the resin temperature in the orifice at 78.degree. C., under otherwise the same conditions as described in Examples 1 to 18, various expanded products are prepared. The results are shown in Table 5, which clearly shows that Examples 28 to 36 give better results than Comparison examples 18 to 21 even when there is employed Resin C of an ethylene-vinyl acetate copolymer with higher vinyl acetate content from which a volatile blowing agent is liable to be readily escaped.
TABLE 8
__________________________________________________________________________
Base resin:
C 100 wt. parts
Nucleators:
Calcium stearate 0.1 wt. parts, calcium silicate 0.6 wt.
parts
Blowing agents:
D: Dichlorodifluoromethane
22 wt. parts
.[.E: 1-chloro-1,1-difluorethane.].
20 .Iadd.wt. .Iaddend.parts
.Iadd.E: 1-chloro-1,1-difluoroethane.Iaddend.
G: 1,2-dichlorotetrafluoroethane
28 wt. parts
H: 1,2-dichlorotetrafluoroethane/mono-chloropentafluoroet
hane = 75/25 (wt. ratio)
26 wt.
__________________________________________________________________________
parts
.[.Blow-.]. Evaluation
.[.ing.].
Density .[.Feeding.].
.[.agent.].
(10 days after
Compressive
50% .[.character-.].
Blowing
expansion
strength
compression
Compression
Surface
agents
g/cm/hu 3
coefficient
permanent set
creep smoothness
__________________________________________________________________________
Additive (wt. parts)
Type of
Example compounds
Trade name
28 Saturated
Amine AB (3.0)
D 0.031 a b b a
29 higher Amine AB (5.0)
E 0.033 a b b a
30 aliphatic
Amine AB (2.0)
amine
31 Saturated
Fatty acid
G 0.037 a b b a
higher amide T (2.0)
D 0.030 a b b a
32 fatty Fatty acid
E 0.032 a b b a
acid amide T (3.0)
33 amine Fatty acid
G 0.038 a b b a
amide T (1.0)
34 Complete
Hardened D 0.030 b b b a
ester of
oil (5.0)
35 saturated
Hardened E 0.033 b b b b
higher oil (8.0)
36 fatty Hardened G 0.038 b b b b
acid oil (3.0)
__________________________________________________________________________
Comparison
example Additives
18 None D 0.084 d d d d
19 None E 0.084 d d d d
20 None G 0.064 d d d d
21 None H 0.032 c c c b
__________________________________________________________________________
Evaluation
.Iadd.Feeding.Iaddend.
Closed
.Iadd.characteristc.Iaddend.
cellular
through
Maximum
Dimensional
characteristic
Overall
extruder
shrinkage
stability
value evaluation
__________________________________________________________________________
Additives (wt. parts)
Type of
Example compounds
Trade name
28 Saturated
Amine AB (3.0)
a a a a a
29 higher Amine AB (5.0)
b a a b a
30 aliphatic
Amine AB (2.0)
amine
31 Saturated
Fatty acid
a a a a a
higher amide T (2.0)
a a a a a
32 fatty Fatty acid
a a a a a
acid amide T (3.0)
33 amine Fatty acid
a a a a a
amide T (1.0)
34 Complete
Hardened b a a a a
ester of
oil (5.0)
35 saturated
Hardened b a a b a
higher oil (8.0)
36 fatty Hardened b a a a a
acid oil (3.0)
__________________________________________________________________________
Comparison
example Additives
18 None a d d b d
19 None a d d b d
20 None a d d b d
21 None a b b d d
__________________________________________________________________________
EXAMPLES 37-39 AND COMPARISON EXAMPLES 22-24
According to the same procedure as in Examples 1-18 except for the specific compounds and their amounts and the amounts of dichlorodifluoromethane as shown in Table 9, various expanded products are prepared. The results as shown in Table 9 indicate that the products of Examples 37-39 are better in expansion moldability and physical properties of the resultant expanded products than those of the Comparative examples even when the amounts of the blowing agent are greatly changed as shown in Table 9.
TABLE 9
__________________________________________________________________________
Resin: B 100 wt. parts
Nucleators:
Calcium stearate 0.1 wt. parts, calcium silicate 0.6
wt. part
Blowing agent:
Dichlorodifluoromethane
Evaluation
Density 50% Feeding Closed
Amount
(10 days
Com- com- Com- charac-
Maxi- cellular
Over-
Additives .Iadd.of .Iaddend.blow-
after ex-
pressive
pression
pres-
Surface
teristic
mum Dimen-
charac-
all
trade name
ing agent
pansion)
strength
perma-
sion
smooth-
through
shrink-
sional
teristic
evalu-
(wt. parts)
(wt. parts)
g/cm.sup.3
coefficient
nent set
creep
ness extruder
age stability
value
ation
__________________________________________________________________________
Example
37 Fatty acid
60 0.014
a b b a b a a a
amide T (4)
38 Fatty acid
9 0.077
a b b a a a a a a
amide T (2)
39 Fatty acid
5 0.174
a a a a a a a a a
amide T (1)
Comparison
.[.60.].
example
22 .Iadd.60.Iaddend.
0.080
d d d d a d d b d
23 9 0.089
c c d d a d b b d
24 5 0.195
b c c c a d c d d
__________________________________________________________________________
EXAMPLE 40
In polyethylene resin (F-2130, trade mark, produced by Asahi-Dow Limited, density: 0.921 g/cc, MI: 3.0 g/10 min.), there are added by kneading 0.45% by weight of dicumyl peroxide as crosslinking agent and 1.5% by weight of stearic acid amide (Fatty acid amide T, trade mark, produced by Kao Soap Co., Ltd.) and the mixture is subjected to crosslinking reaction. The resultant crosslinked polyethylene resin particles (spherical with diameter of 1.5 mm) with gel content of 61% are impregnated in an autoclave with dichlorodifluoromethane under pressurization with heating and thereafter cooled. The expandable crosslinked polyethylene resin particles thus obtained are found to contain 14 wt. % of dichlorodifluoromethane. These particles are placed in a pressure-type expanding vessel wherein they are allowed to expand while passing steam of 0.23 Kg/cm.sup.2 .multidot.G for 45 seconds to obtain primarily expanded particles with density of 100 Kg/m.sup.3. Subsequently, these primarily expanded particles are placed in an autoclave and, under pressurization with the air at 10 Kg/cm.sup.2 .multidot.G, heat treatment is conducted at 80.degree. C. for 15 hours to increase inner pressure in the cells, followed by passing of steam of 0.32 Kg/cm.sup.2 to effect expansion to obtain secondarily expanded particles with density of 27 Kg/m.sup.3. After increasing the inner pressure in the cells of these secondarily expanded particles, they are filled under compression in a cavity in a molding machine (ECHO-120 model, produced by Toyo Machinery & Metal Co., Ltd.) and subjected to expansion fusion molding by heating with steam of 1.1 Kg/cm.sup.2 .multidot.G. The density of the molded expanded product is found to be 25 Kg/m.sup.3 and have a closed cellular characteristic value of less than 0.01.
COMPARISON EXAMPLE 25Example 40 is repeated except that no stearic acid amide is added. The resultant primarily expanded particles are found to have a density of 111 Kg/m.sup.3, while the secondarily expanded articles a density of 31 Kg/m.sup.3. The expanded particles have higher density as compared with those of Example 40 and said particles are found to have relatively large number of creases. When the secondarily expanded particles are molded similarly as in Example 40, the expanded product obtained is found to have a density of 30 Kg/m.sup.3. It is also inferior in closed cell percentage and compressive strength to that of Example 40. The life of beads impregnated with blowing agent for retaining desirable expandability is also shorter by one hour as compared with those of Example 40.
EXAMPLE 41Using a mixed resin comprising 60 parts by weight of a high density polyethylene (Suntec S-360, trade mark, produced by Asahi Kasei Kogyo Kabushiki Kaisha, density: 0.950 g/cc) and 40 parts by weight of an ionomer (Surlyn A 1706, trade mark, produced by E. I. du Pont de Nemours, Inc.), 1.5 parts by weight of stearic acid amide as specific additive (Fatty acid amide T, trade mark, produced by Kao Soap Co., Ltd.), 0.3 part by weight of calcium silicate powders as nucleators and 27 parts by weight of dichlorodifluoromethane as volatile blowing agent are kneaded with said mixed resin in a 30 mm single screw extruder equipped with an orifice with diameter of 5 mm and heated at 220.degree. C. While adjusting the resin temperature in the orifice at 122.degree. C., extrusion expansion is conducted to obtain expanded product having excellent characteristics such as closed cellular characteristic of 0.005 g/cm.sup.3, density of 23 Kg/m.sup.3, compressive strength coefficient of 2.01.times.10.sup.-2 and maximum expansion shrinkage of 0.2%.
EXAMPLE 42Example 41 is repeated except that the base resin of high density polyethylene is replaced by isotactic polypropylene (Chisso Polypro 1011, trade mark, produced by Chisso Corporation) and the resin temperature in the orifice is adjusted at 135.degree. C. The expanded product obtained is found to have excellent characteristics such as closed cellular characteristic. Of 0.008 g/cm.sup.3, density of 21 Kg/m.sup.3, compressive strength coefficient of 2.10.times.10.sup.-2 and maximum expansion shrinkage of 0.1%.
Claims
groups are eliminated..].. 2. An expanded article according to claim 1, wherein the.[.polyolefin resin is a.]. olefin polymer is a polyethylene resin or an ethylenevinyl acetate copolymer resin..[.3. A process for expanding an olefin polymer, which comprises incorporating at least one compound, which imparts little shrinkage to said expanded polymer after expansion, selected from the group consisting of the compounds of the formulas (I), (II) and (III) as set forth below in a thermoplastic synthetic resin in an amount of 0.1 to 10% by weight based on the weight of said resin together with a blowing agent under the condition maintained at a temperature in the range from about 15.degree. to 300.degree. C. to form an expandable resin composition and then allowing said resin composition to expand utilizing the expanding force of the blowing agent contained therein: ##STR15## wherein R.sub.1 is an alkyl group having 10 to 24 carbon atoms, X and X' each hydrogen atom, an alkyl group having 1 to 24 carbon atoms which may be substituted or a substituent selected from the group consisting of --(CH.sub.2).sub.n NH.sub.2 wherein n is an integer of 1 to 22, ##STR16## wherein R.sub.5 is an alkyl having 1 to 24 carbon atoms, --(R.sub.4 O).sub.m H wherein R.sub.4 is an alkylene group having 1 to 5 carbon atoms and m is an integer of 1 to 10, ##STR17## wherein R.sub.5 is an alkyl having 1 to 24 carbon atoms, ##STR18## wherein n is an integer of 1 to 22 and A is hydrogen atom or ##STR19## wherein A' is hydrogen atom or ##STR20## wherein R.sub.2 is an alkyl group having 9 to 23 carbon atoms, Y and Y' each hydrogen atom, an alkyl having 1 to 24 carbon atoms, an acyl having 10 to 24 carbon atoms or a substituent of the formula --(R.sub.4 O).sub.m A.sub.2 wherein A.sub.2 is hydrogen atom, an alkyl having 1 to 24 carbon atoms or acyl having 10 to 24 carbon atoms; ##STR21## wherein [R.sub.3 ] means plural alkyl or hydroxyalkyl groups corresponding in number to the integer l, which may be the same or different, each having 9 to 23 carbon atoms, R.sub.4 an alkylene group having 1 to 5 carbon atoms, k an integer of 0 to 7, l an integer of 2 to 8 and Z a l-valent residue of l-valent polyhydric alcohol from which l hydroxyl
groups are eliminated..]. 4. A process according to claim.[.3,.]..Iadd.8
.Iaddend.wherein the olefin polymer is cross-linked. 5. A process according to claim.[.3,.]..Iadd.8.Iaddend.wherein the olefin polymer is a polyethylene resin, an ethylene-vinyl acetate copolymer resin, or a
polypropylene resin. 6. A process according to any of claims.[.3.]..Iadd.8.Iaddend.to 5, wherein the polymer composition is expanded by
extrusion foaming by means of an extruder..Iadd.7. An expanded article of an olefin polymer composition comprising an olefin polymer and at least one compound, which reduces shrinkage of said expanded article after expansion, selected from the group consisting of the amide or complete ester compounds represented by the formula (II) or (III), respectively, as set forth below in an amount of 0.1 to 10 percent by weight based on the weight of said olefin polymer and having a closed cellular characteristic value of 0 to 0.5 g/cm.sup.3, a bulk density of 10 to 200 kg/m.sup.3 and a compressive strength coefficient of 2.15.times.10.sup.-3 to 2.89.times.10.sup.-2: ##STR22##.Iaddend. wherein R.sub.2 is an alkyl group having 9 to 23 carbon atoms, Y and Y' each is a hydrogen atom, an alkyl having 1 to 24 carbon atoms, an acyl having 10 to 24 carbon atoms or a substituent of the formula --(R.sub.4 O).sub.m A.sub.2 wherein R.sub.4 is an alkylene group having 1 to 5 carbon atoms, m is an integer of 1 to 10, and A.sub.2 is hydrogen atom, an alkyl having 1 to 24 carbon atoms or acyl having 10 to 24 carbon atoms; ##STR23## wherein [R.sub.3 ] means plural alkyl or hydroxyalkyl groups corresponding in number to the integer l, which may be the same or different, each having 9 to 23 carbon atoms, R.sub.4 is an alkylene group having 1 to 5 carbon atoms, k is an integer of 0 to 7, l is an integer of 2 to 8 and Z is an l-valent residue of an l-valent polyhydric alcohol of the formula Z(OH).sub.l from which l hydroxyl groups are eliminated; said expanded article having been prepared by the use of a volatile organic blowing
agent..Iadd.8. A process for expanding an olefin polymer, which comprises incorporating at least one compound, which reduces shrinkage of the resulting expanded polymer after expansion, selected from the group consisting of the amide or complete ester compounds of the formula (II) or (III), respectively, as set forth below into the olefin polymer to be expanded in an amount of 0.1 to 10 percent by weight based on the weight of said olfein polymer together with a volatile organic blowing agent under the condition maintained at a temperature in the range of from about 15.degree. to 300.degree. C. to form an expandable resin composition and then allowing said expandable resin composition to expand utilizing the expanding force of the blowing agent contained therein: ##STR24##.Iaddend. wherein R.sub.2 is an alkyl group having 9 to 23 carbon atoms, Y and Y' each is a hydrogen atom, an alkyl having 1 to 24 carbon atoms, an acyl having 10 to 24 carbon atoms or a substituent of the formula --(R.sub.4 O).sub.m A.sub.2 wherein R.sub.4 is an alkylene group having 1 to 5 carbon atoms, m is an integer of 1 to 10, and A.sub.2 is hydrogen atom, an alkyl having 1 to 24 carbon atoms or acyl having 10 to 24 carbon atoms; ##STR25## wherein [R.sub.3 ] means plural alkyl or hydroxyalkyl groups corresponding in number to the integer l, which may be the same or different, each having 9 to 23 carbon atoms, R.sub.4 is an alkylene group having 1 to 5 carbon atoms, k is an integer of 0 to 7, l is an integer of 2 to 8 and Z is an l-valent residue of an l-valent polyhydric alcohol of the formula Z(OH).sub.l from which l hydroxyl groups are eliminated.
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Type: Grant
Filed: Jun 8, 1981
Date of Patent: Nov 20, 1984
Assignee: Asahi-Dow Limited (Tokyo)
Inventors: Seizaburo Watanabe (Suzuka), Yutaka Matsuki (Suzuka)
Primary Examiner: Morton Foelak
Application Number: 6/271,067
International Classification: C08J 914;
