JPS58208330A - Polyolefin composition for highly expanded foam - Google Patents

Abstract

PURPOSE:The titled polyolefin composition capable of forming highly expanded foam having a uniform cell structure and excellent appearance, containing a volatile organic blowing agent, a specified amine and a specified amide. CONSTITUTION:Use is made of an amine of formula I (wherein R1 is a 1-5 C alkylene, Acyl is H or an acyl, n is 1-10, and X is 0-2), e.g., 2-hydroxyethylamine, and an amide of formula II (wherein R2 is a 1-5 C alkylene, R3 is a 1- 23 C hydrocarbon group, m is 1-10, and y is 0 or 1), e.g., N-mono-2-hydroxyethylhexanamide. Namely, 100pts.wt. (A) polyolefin, preferably, high-density polyethylene having a HMI <= about 30g/10min and a swell value <= about 30g/ 10cm, is mixed with about 5-80pts.wt. volatile blowing agent (e.g., dichlorotetrafluoroethane/methyl chloride mixture) and about 0.05-15pts.wt. (total amount) above amine and amide.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition for highly foamed polyolefin materials, and more particularly to a composition for highly foamed polyolefin materials comprising a polyolefin, a volatile organic blowing agent, a specific amine, and an amide.

Until now, it has been known to obtain a polyolefin foam molded product by adding a volatile organic foaming agent to a non-crosslinked conventional polyolefin and carrying out extrusion foaming. Widely used as buffering material, packaging material, etc.

However, in general, polyolefins have low viscoelasticity when melted by heating and cannot sufficiently maintain the gas pressure of the blowing agent, so they collapse when the formed cells become large enough.
Due to heat generation during cooling and crystallization, the cells cannot be cooled and solidified smoothly.As the foaming agent has high permeability to the scum, it easily evaporates when it evaporates, preventing sufficient foaming.
However, it is difficult to obtain a highly foamed product with a homogeneous cell structure and good appearance.

For example, the methods proposed so far (Special Public Interest Publications 1973-
43.11), the foaming conditions that allow for high foaming are limited to a very narrow range, and it is difficult to control these foaming conditions over a long period of time, and special equipment is required. Therefore, it cannot be said that it is necessarily a satisfactory method for industrial implementation.

To solve these problems, in order to make a polyolefin into a highly foamed molded product with a foaming rate of about 5 times or more, the polyolefin must be treated with peroxide or radiation in advance to crosslink it. A method of foam molding has been proposed, but this requires a special process for crosslinking, which inevitably increases the cost of the product.

On the other hand, polyethylene with a high degree of crystallinity, such as high-density polyethylene, has a large viscoelastic change near the melting point compared to low-density polyethylene, so the extrusion temperature range is significantly restricted, and it It becomes more difficult to maintain proper conditions and controls for continuous extrusion for foam purposes. In addition, since Hatake density polyethylene has a higher degree of crystallinity than 1 low density polyethylene, it generates a large amount of heat during the crystallization described above, and assimilation of the cells during cooling is further hindered, resulting in less destructive deformation of the cells. This results in decreased extrusion moldability and product quality deterioration. In general, the thicker the foam, the more heat buildup during crystallization becomes a concern, and the more difficult it is for the cells to cool and assimilate, making this tendency more severe. Furthermore, while low-density polyethylene has long chain branches and high melt viscoelasticity, high-density polyethylene has long chain branches and has low melt viscoelasticity, so it is extruded from a die with a foaming agent and foam-molded. In some cases, the die cannot exhibit sufficient pressure resistance to suppress the generation of bubbles, and the cells already formed in the die are destroyed by heat and shear force during the extrusion foaming process, resulting in foaming. It causes deterioration of the quality of the body. This tends to increase as the cross-sectional area of the die opening increases, that is, as the thickness of the foam increases. To solve this problem, it is possible to increase the resin pressure by increasing the extrusion rate. Extremely special equipment with capacity must be used, and if the extrusion rate is excessively increased, flow disturbances such as melt fractures will occur and extrusion moldability will deteriorate, which is impractical.

In this way, none of the methods known so far for producing high-quality, highly foamed molded products using polyethylene as a raw material are necessarily satisfactory as industrially practicable methods. I couldn't say that.

The present inventors have conducted intensive research to obtain highly foamed molded products with excellent appearance and homogeneous cell structure using non-crosslinked polyethylene, particularly high-density polyethylene, as a raw material. The inventors have found that the object can be achieved by using a combination of amines and amides, and based on this knowledge, the present invention has been completed.

That is, the present invention provides (a) a polyolefin, (b) a volatile organic blowing agent, at least one of the amines represented by (·→-general formula %(1) is an integer of 1 to 2), and ( At least one kind of amide represented by the following formula: R2 is an alkylene group having 1 to 5 carbon atoms, R3 is a hydrocarbon group having 1 to 23 carbon atoms, m is an integer of 1 to 10, and y is O or 1. The present invention provides a composition for a highly foamed polyolefin body comprising:

In the composition of the present invention, the above-mentioned (c) is used as a foaming modifier.
It is necessary to use a combination of an amine represented by the general formula (1) as a component and an amide represented by the general formula (11) as a component. These amnes and amides are both known compounds or can be easily produced according to known methods. Examples of such amines include 2-hydroxyethylamine, di-2-hydroxyethylamine, tri-2-hydroxyethylamine,
-Hydroginzolobylamine, di-2-hydroquinepropyl-rmine, 1-2-hydroginezolobylamine, 3
-Hydroginzolobylamine, di-3-hydroginzolobylamine, tri;3-hydroginzolobylamine,
tripolyoxy/ethylamine and ester compounds of these with fatty acids, such as] 2-hydroxyethylamine monostearate, di-2-hydroxyethylamine cisdearate, tri2-hydroxyethylamine tristearate, tri2- Examples include hydroxyethylamine monolaurylate-1., tri-2-hydroxyethylamine dilaurylate-1., and tri-2-hydroquinethylamine trilaurylate. Particularly preferred are 2-hydroquinethylamine, di-2-hydroxyethylamine, tri-2-hydroquinethylamine, 2-hydroginezolobylamine, c-2-hydroginezolobylamine, tri-2-hydroginezolobylamine. Such as amines. These amines may be used alone or in combination of two or more.

Examples of amides include N-2-hydroxy/ethyl-hexanamide, N-2-hydroxy-7ethyl-octanamide, N-2-hydroxyethyl-decaneamide, N-2-hydroxy Ethyldodecanamide, N-2
-Hydroxyethyl-telatecanamide, N-2-hydroxyethyl-hexadecanamide, N-2-hydroxy/nibu-ruoctadecaneamide, N,N-di-2-hydrogynethyl-hexanamide, N,N-di2 -Hydroquinethyl-octanamide, N,N-di2-hydroquine/ethyl-decaneamide, N,N-di2
-Hydroxy/ethyl-dodecanamide, N,N-2-hydroxy/ethyl-tetradecanamide, N,+q-di-2-hydroxy/ethyl-hexadecaneamide, N,N-
Di-2-hydroxyethyl-octatecanamide, N-
Mono-2-hydroxypropyl-hexanamide, N-
Mono-2-hydroxy/propyl-octanamide, N-
Mono-2-hydroxypropyl-decanamide, N-mono-2-hydroxypropyl-dotecanamide, N-mono-2-hydroxypropyl-tetradecanamide IN
-Mono-2-hydroxy/propyl-hexadocanamide, N-mono-2-hydroginepropino-1-oftatecanamide, N,N-di-2-hydro-propyl-hexaneamide, N,N-di 2-human mouth/propyl-octanamide, N,N-di-2-hydroxybrobyrudecanamide, N,N-di-2-hydroxybrovir-tetra tecanamide, N,N-di-2-hydroxypropyl-hexadecanamide, N,N-di-2-hydroxypropyl-octatecanamide, polyoxy/ethylenehexanamide, polyoxyethyleneoctanamide, polyoxy/ethylenedecaneamide, Examples include polyoxyethylene dodecane amide, polyoxyethylene tetradecane amide, polyoxy/ethylene hexatecan amide, polyogine ethylene octadecane amide, etc., but particularly preferable ones include N-mono-(and N, N
-di) 2-hydroquinethyl-hexanamide, N-
Mono-(and N,N-di) 2-hydroxy/ethyl-octanamide, N-mono-(and N,N-di) 2-hydroxy-7ethyldotecanamide, and
&hiN,N-c) 2-Hydroxypropyl-\xa/amide, N-mono-(and N,N-di) 2-hydroxypropyl-\xa/amide,
N,N-c) 2-hydroxybropyruttecan amide and the like. These may be used alone or
Also, two or more types may be used in combination.

The ratio of the amines (0) to the amides (component) is 1:4 to 4:1, preferably 3 to 7.
::Used in the range of 3. In addition, these compound rats are
The total amount of amines and amides is selected to be within the range of 0.0 to 15 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the polyolefin component (a). If this ambiguity is less than 0.05 parts by weight, a foam with good cell distribution and suitability for thick materials cannot be obtained, and if it exceeds 15 parts by weight, the air bubble distribution becomes uneven and It causes a plasticizing effect, leading to quality deterioration of the foam.

Component (a), ie, polyolefin, used in the composition of the present invention includes, for example, polyethylene, polypropylene, polybutene-1,1,2-polybutadiene,
-Polybutadiene, ethylene/-zolopylene copolymer, copolymer of ethylene or propylene with other α-olefins, or ethylene-vinyl acetate copolymer, ethylene-ethyl-γ acrylate copolymer, ethylene-j-fertilized Vinyl copolymer, ethylene ionomer (ethylene-
Copolymers whose main component is ethylene, such as metal salts of copolymers of ethylene and unsaturated carboxylic acids, such as zinc or sodium salts of acrylic acid copolymers,
Among these, high-density polyethylene with both degrees of 0 and 930 y/'cA or more is preferred, and especially HMI3or/+o
High-density polyethylene with a swell value of 30 F/10 tM or less and a swell value of 30 F/10 tM or less is suitable.

In the composition of the present invention, these polyethylenes may be used alone, or may be used as a mixture of two or more crushed polyethylenes, and the polyolefin of Kosai et al. It is also possible to use a mixture of these as appropriate.

Components used in the composition of the present invention, that is, volatile organic blowing agents, include, for example, hydrocarbons, logenated hydrocarbons, and specific examples of these hydrocarbons include haflopane, butane, pentane, pentene, hexane, etc. But still...
Specific examples of hydrocarbons include methyl chloride, methane dichloride, trichloromonofluoroethane, dichlorodifluoromethane, monochlorotrifluoromethane, dichloromonofluoromethane, monochlorodifluoromethane,
1.1,2. -1 Lichlorotrifluoroethane, l, 2
-dichlorotetrafluoroethane, monochloropentafluoroethane, etc. Among these, preferred blowing agents are mixed blowing agents consisting of 1,2-dichlorotetrafluoroethane and other 7-logenated hydrocarbons, and particularly preferred among these 7-logenated hydrocarbons are Trichloromonofluoromethane, /chloromonofluoromethane, dichlorodifluoromethane, l, I, 2-
) At least one halogenated hydrocarbon selected from dichlorotrifluoromethane, methylene chloride, and dichlormethane. 1, 2- in this mixed blowing agent
The mixing ratio of monodichlorotetrafluoroethane and other non-logenated hydrocarbons is 1:4 to 1 in molar ratio.
:I is desirable, preferably from 3:F to 7:3.
is within the range of

The mixing ratio of the volatile blowing agent in the composition of the present invention is preferably in the range of 5 to 80 parts by weight, more preferably in the range of 10 to 60 parts by weight, per 100 parts by weight of polyolefin. If the amount is less than 80 parts by weight, it is difficult to obtain a highly foamed product, and if the amount exceeds 80 parts by weight, the foaming ratio will not increase much even if the mixing amount is increased, making it uneconomical, and furthermore, the quality of the foam may deteriorate. lead to deterioration.

Particularly suitable as the composition of the present invention is I(lvli;
The temperature is less than or equal to +o minutes, preferably less than 20 degrees/10 minutes, and the swell value is less than or equal to 30f/10z, preferably it
1,2-dichlorotetrafluoroethane as a volatile organic blowing agent and other halogenated hydrocarbons such as trichloromonofluoromethane, dichloromonofluoromethane, dichlorodifluoromethane% for high density polyethylene up to 25it'/10 cm. 11112-
A combination of at least one selected from trichlorotrifluoroethane, methyl chloride, and dichloride methane, and the above-mentioned amines of general formula (1) and amides of general formula (11). A certain composition of the present invention may contain a commonly used cell nucleating agent, if necessary. Examples of this bubble nucleating agent include inorganic fine powders such as talc and silicon oxide, organic fine powders such as sacrificial lead stearate and calcium/umium stearate, and gases produced by heating such as citric acid and sodium hydrogen carbonate. In addition, ultraviolet absorbers, antioxidants, antistatic agents, colorants, etc. may be included as desired.

To prepare the composition of the present invention, the components (a) to (a) and predetermined amounts of additional components added as necessary are mixed by any method commonly used for preparing a homogeneous mixture. do. Particularly suitable are the masterbatch method and the triblend method. Although there is no particular restriction on the order of addition of each component, a method is usually used in which components other than the volatile organic blowing agent are mixed in advance and then this blowing agent is mixed in during the extrusion foaming process.

As a method for producing a foam from the composition of the present invention, for example, a method is usually used in which the composition is prepared under high temperature and high pressure, and then exposed to a low temperature and low pressure region to form a foam. As the molding method at this time, for example, an extrusion foaming method, a press foaming method, an injection foaming method, an in-mold foaming method, etc. can be applied, but the extrusion foaming method is advantageous.

In this way, extruded foam molded articles of various shapes, such as notebooks, boats, rods, tubes, nonoiso, nets, etc., can be manufactured.

The foam obtained from the composition of the present invention is a high foam with an expansion ratio of 5 to 100 times, and has excellent heat insulation and cushioning properties, and can be used as a heat insulating material, a cushioning material, and a packaging material. It is commercially available as such.

Note that the HMI and swell value have the following meanings.

(1) HMI: It is a measure of emplacement of a resin fluid group under certain conditions! 11. Extruded based on J Engineering 5K6760 at a temperature of 15) 0±0.5°C, a load of 2+, and 6 kg, and is expressed as the extrusion weight per 10 minutes. It is used as an indicator of the viscous properties of molten resin.

(2) Swell value 2 caliber 40mmφ (/linder length/cylinder diameter -25, screw compression ratio -3,2) Inner diameter 21 cylinder φ installed in F direction at the tip of the extruder, outer f12
5 mmφ annular die, screw rotation speed 100
r p m *A tube-shaped resin is extruded at a temperature of 230° C., cut into a length of 1 ocrn downward from the die, and its weight is measured to determine the swell value. The unit is 2/1(]c
v de no 1 squirrel. In other words, it is the weight per unit length of the resin extruded under special rectangular conditions, and indicates the elastic properties of the molten resin.The larger this value is, the greater the elastic properties are.Next, Examples The present invention will be explained in more detail below.

In addition, each physical property of the foam in Examples was evaluated according to the following criteria.

(1) Four-shaped appearance Observe the appearance of the foam and evaluate it according to the following criteria.

A. There is no uneven foaming such as twisting or unevenness in the foam, and
The surface has excellent smoothness without ripples or wrinkles.

B: There is no foaming irregularity such as 711 thickness and unevenness in the foam, but there are ripple-like wrinkles on the surface, which is durable enough to be used as a product.

C: Uneven foaming with twisting and unevenness was observed in the foam.
Items whose value as a product is significantly inferior.

(2) Observe the bubbles in the cell distribution foam and evaluate them according to the following criteria: A...
"Ship with uniform air bubble distribution."

B. If the somewhat uneven distribution has value as a product.

C.-Voids are observed to a slightly non-uniform degree and very non-uniform. Product value is extremely low.

(3)! f Shrinkage recovery, based on the compression test method shown in O8Z-0231, the test piece was compressed to 50% of the early stage υ, the load was gradually removed, and it was left for 30 seconds to recover the thickness. Wait until then, and then perform another 50% compression test on the thickness of the recovered body in the same manner. This operation is repeated 5 times, and the white fraction of the value obtained by dividing the recovered thickness of the 5th time by the initial thickness is evaluated. The evaluation criteria for the buffering properties (cushioning properties) are as follows.

Δ Less than 10%. Extremely excellent.

1, + -] Range of 0 to 20%. Are better.

North of L4-20%, the amount of deformation due to buckling is large and the value as a product is inferior.

(4) Expansion ratio Foam electricity storage was calculated from the weight and volume of the foam 10 days after foaming based on JIS K-6767, and the expansion ratio was determined according to the following formula.

(5) As an indicator for determining how efficiently a foam with a large thickness and a large cross-sectional area can be obtained with respect to the appropriate extrusion rate for thick materials, the efficiency calculated according to the following formula is used. use

The degree of foam cross-sectional area is Ca, and the unit of extrusion amount is K.
y/time.

The greater the efficiency, the greater the expansion ratio in the direction perpendicular to the extrusion direction than in the extrusion direction, and a foam with a large cross-sectional area can be obtained with a small extrusion 111, making it suitable for molding thick objects. It turns out.

The evaluation criteria are as follows.

A. It has an efficiency of 0.12 l- or more and is most suitable for molding thick materials.

B... Efficiency is 0.08 or more and less than 0.12, and although the efficiency is slightly inferior, thick material forming Vi is possible,
It's practical.

C: Efficiency is less than 0.08, making it difficult to mold thick materials.

Furthermore, the abbreviations of compounds used in each example have meanings not shown in the table below.

Example 1 100 parts by weight of high-density polyethylene HDPK-1 were mixed with amines and amides of the type and amount shown in Table 1, dispersed in a mixed wire ink bottle until they were evenly distributed, and then extruded into foam. Directions Materials were prepared. Next, a first extruder (NZ50 rating φ, L/D=30
) and a second extruder (1 diameter 65 cylinder φ, L/D-30) equipped with a cooling oil jacket and a 7 linter connected in series. of extruded foam base material at a speed of 5.0 kg/hour up to 2
H
-111 and R-113 are injected at a ratio of 4116 parts by weight per 100 parts by weight of resin to prepare a composition for high foaming. This composition was supplied to a second extruder through a connecting pipe, where it was gradually cooled to - to the optimum temperature for foaming, and extruded through a rod die having an inner diameter of 5 m++φ.

A foam was produced.

The physical properties of the foam obtained by VCL are shown in Table 1.For comparison, a foam was produced in the same manner as above using a composition that did not contain amines and Ami-F. , and its physical properties are also listed in Table 1.

As is clear from this table, the foams obtained by blending amines and amides are both low in density and foam at extremely high expansion ratios, and their appearance also shows uneven foaming and
The result is a very good product with no 7 points. -Also, the bubble distribution is uniform throughout and no voids are observed.
The compression recovery rate was rarely less than 10%.

On the other hand, if 1. amine and amide are not blended,
It was foamed at a high magnification with low crystallinity, and although the appearance was excellent with no foaming or unevenness, the bubble distribution was uneven, many voids were observed, and the compression recovery rate was 20% or more. .

Example 2 As a polyolefin, 1 month + L God knee 111,
For that +oo1i groin, foaming agent) (13 of -113
0 parts by weight were added, all <Example 1>
A composition similar to the above was prepared and foam-molded. The physical properties of the foam thus obtained are shown in Table 2.

As is clear from this table, when amines and amides are blended, foams that exhibit low density, foam at high expansion ratios, and have excellent appearance properties, cell distribution, and compression recovery properties are obtained. Ta.

On the other hand, when amine and amide are not blended, the result is a foam with a low density, but the appearance is foamy (foamed), the pores are noticeably distorted, the bubble distribution is uneven, and there are many voids. Moreover, the compression recovery rate was 20% or more -F, and the commercial price was low.

Example 3 All examples were the same except that the mixture of amine [with] and amide (di) in 1:1 East-Nyl was changed in the range of 0.03 to +8!f'f-M part. In the same manner, a paraboloid was prepared and then heated and foamed.The physical properties of the foamed body thus obtained were applied to the third layer.

As is clear from this table, the mixtures of amine and amide used in an amount of 0.07 to 13% have low crystallinity and high foaming ratio, and have good appearance properties, bubble distribution, and compression recovery properties. However, when the amount of amine used is 0.03 parts by weight, the bubble distribution and compression recovery properties are poor, and when the amount of amine used is 18 parts by weight, the appearance properties and compression recovery properties are poor.

Example 1 Different types of polyolefins were used. Per 100 parts by weight of A and C, two parts of a 1:1 mixture of amine [with] and amide ◎ and 16 parts of each of Rl 14 and J (-113) were added. A foaming composition was prepared in the same manner as in Example 1 by blending parts by weight, and then foam molded.The physical properties of the obtained foam are shown in Table 4.

For comparison, results for a composition containing no amine or amide are also shown.

As is evident from this table, the foams obtained from compositions containing amines and amides exhibit high magnification at low density;
Although the appearance properties, bubble distribution, and compression recovery properties were good,
When the amine and amide were not included, although the density was low and the magnification was high, other physical properties were poor.

Example 5 Different types of volatile organic blowing agents were used: one with 30 tons of foam mixed with 2 parts by weight of a 1:1 mixture of amine and amide (T), and one without. thing A
A foam was produced in the same manner as in Example 2. Table 5 shows the properties of each foam thus obtained.

As is clear from this table, in all cases of foams containing amines and amides, the foams exhibit low density and still have a high culture rate, and are excellent in appearance properties, cell distribution, and compression recovery properties. It had high commercial value. On the other hand, when amine and amide are not included, although the density is low and the foaming rate is high, the appearance is markedly uneven foaming, the bubble distribution is uneven, and many voids are observed. The recovery rate was 20% or more, and the commercial value was extremely poor overall.

Example 6 Various high-density polyethylenes were used as polyolefins, and amines (grain and amide) were added to the 1004i
A base material for foam molding was prepared by adding 0.6 ml/t part by weight of fused silicon as a nucleating agent and triblending with a Hen/Nil mixer.

The first extruder has a blowing agent inlet in the cylinder (diameter 50 x φ, L/1 = 30), and the second extruder has a cooling I11 oil jacket in the cylinder (diameter 05).
Using an extrusion/foaming device having a structure in which diaphragms φ, L/D=: 30) were connected in series, the base material was fed into the first extruder heated to a maximum temperature of 220° C. for 71°C at a feed rate of +oK9/hour. tt
A foaming composition is prepared by injecting a specified foaming agent into the zone where C is fed and melt-kneaded. This foaming agent is a mixture of F I + 4 and F] 13 in an equimolar ratio. High-density polyethylene 10 I) was continuously supplied to the municipal finance department at a rate of 35 stacked parts using a high-pressure pump. The composition thus obtained was supplied to the second extruder through a connecting pipe, where it was gradually cooled down to the optimum temperature. , and was extruded through a 5 mmφ rod die to obtain a foam. The evaluation results of the obtained foams are summarized in Table 6. All foams have a high expansion ratio of about 10 times, and have good evaluation items such as cell distribution, compression recovery, and extrusion moldability, and are suitable for thick materials.
It was also in good condition and had sufficient commercial value.

As is clear from this table, HMI is 3or/+.

Particularly good binding is obtained when high density polyethylene with a swell value of less than 30 SF/'l Ocm is used.

In this case, if HM and T are larger than 30 r/I 0 min, voids will occur and the bubble distribution will be uniform, and - if the swell 1 shift is smaller than 30 f/l 0 cm. If it stays in January, it tends to cause screws and unevenness.

Example 7 HDPE-1 ('HM-3.8f) as polyolefin
/10 minutes, swell value 20 il/IOcm)
Amine ■ and amide ■
etc. The mixture is mixed with O~20 parts and Fll as blowing agent.
A foam was produced in the same manner as in Example 6 from a foaming composition prepared by adding 35 parts by weight of an equimolar mixture of F113 and F113. Table 7 shows the evaluation results for this foam.
] Besu.

) -・１〇- As can be seen from this table, when amine and Ryomid are not used for a period of time (experiment number 41), the bubble distribution is poor and suitability for thick materials is poor, and commercial value is not recognized [7, When the usability exceeds 15 parts per 100 parts of polyethylene (experiment number 48), the resulting foam has uneven cell distribution and poor compression recovery.

Example 8 A composition was prepared in exactly the same manner as in Example 7, except that a different combination of amine and amide was used. Shown in the table.

/ /'' As is clear from this table, foams with high magnification and excellent properties can be obtained no matter which combination is used.

Example 0 High Wideg HrlPE I
, II"3.8f'710 minutes, swell value 209/]
Example 6 A foam was produced in the same manner. The evaluation results of this foam are shown in Table 9.

// 2. /' Table 9 Example 10 High density polyethylene (HDPE-1, HMx: 3Js
9/1 (1 minute, swell value 20y/+o min) To 100 tons of ridge, add 2 parts of amine (cotton and amide), foaming agent, L2, Flll and F113. A foaming composition was prepared using the foaming composition 7, and a foam was produced in the same manner as in Example 6. The evaluation results of this foam were summarized in the 10th on the table)■
Susu.

Table 10 As can be seen from this table, if the blowing force of the blowing agent is low, the resulting foam will have a low magnification and low compression recovery properties, and if the blowing agent is used in a large amount, the cell distribution will be poor in suitability for thick materials. It becomes a foam.

Patent Applicant Asahi Kasei Kogyo Co., Ltd. Agent Akira Akira Procedure ゛Amendment Show + July 21, 1157''l・lf'1fl,・), Patent Application No. 92371 of 1982! Inin Ai II, (fl Composition No. for Polyolefin Highly Foamed Materials Hb 11 '6 Name I Seal 1 U, '1l VJIf Patent Applicant fij
l'li 1-2-6 Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture,
, (003) Asahi Kasei Industries Co., Ltd. Representative Teru Miyazaki 1 Deputy Director K 104 Higashi 1ij, 4-5 Toya Bldg.
) [Yo Akuseko 0 draw + l'l i 'l increase 1n
rlrusaaki1'lh.

7 Sleeve 1', t/+ 1.1 Elephant Claims column of the specification.

and a column for detailed description of the invention. 8. Contents of amendment 11) The scope of patent claims will be amended as shown in the attached sheet.

(2) "Tripolyoquinoetheramine" on the bottom line of page 8 of the specification will be corrected to "Tripolyoxyethyleneamine."

(3) rl on page 14, line 8 and lines 5 to 4 from the bottom
, t, 2-trichlorotrifluoroethane" is corrected to "trichlorotrifluoroethane."

(4) "1,2-dichlorotetrafluoroethane" in lines 8-9, lines 11-12, and lines 19-20 on page 14 will be corrected to "dichlorotetrafluoroethane."

(5) "1,2-dichlorotetrafluoroethane" on page 15, lines 16-17 will be corrected to "dichlorotetrafluoroethane."

(6) 2 to 1 lines from the bottom of page 15, rl, 1.
2-Trichlorotrifluoroethanej'er l-
IJ Chlorotrifluoroethane".

(7) Change “less than 10%” to “9” in the fourth line of page 20.
Corrected to 0% or more.

(8) Correct and edit the 5th line of page 20 to read "10 to 20% range. jtr 80 to 90% range."

(9) In the 6th line of page 20, change “20% or more” to “
Corrected to "Less than 80%."

01 Add all of the following sentences by starting the third line from the bottom on page 21.

"C6) Extrusion moldability Observing the shape of the foam obtained by extrusion foaming,
Judgment will be made based on the following evaluation criteria.

A: The extrusion state that closely reproduces the shape of the die is maintained continuously, the foam shape has no irregularities such as unevenness or twisting, and the surface is smooth.

B: The extrusion state that reproduces the die mold continues continuously, but small scale-like wrinkles are observed on the surface. It has commercial value.

C: Continuous pressing that reproduces the die mold [t] was difficult due to twisting of the foam, generation of unevenness, or deformation due to shrinkage. It has almost no commercial value. ” 0υ In the table on page 23, “Sunlac M700E” in the fourth line from the bottom of the product name column in the polyolefin resin section will be corrected to “Santic M700KJ.”

0 proverb ``Less than 10%'' in the 7th line of P. 28 of the same book is ``
Corrected to 90% or more.

01 Correct "20% or more" in line 12 of page 28 to "less than 80%".

04 Change “20% or more” in the 9th line of page 30 to “
I will correct it to "less than 80%."

0υ page 36, line 9] of “20% or more”
I will correct it to "less than 80%."

O→ Correct "Henschel mixer" in the 6th line from the bottom of page 36 to "Henschel mixer".

Claim 1 (a) polyolenoin, (b) volatile organic blowing agent,
(c) General formula % Formula % (1) (R3 in the formula is % alkylene having 1 to 5 carbon atoms, AcyL
is a hydrogen atom or a group, n is an integer of 1 to IO, and X is O or an integer of 1 to 2.
(wherein R2 is an alkylene group having 1 to 5 carbon atoms, R1 is a hydrocarbon group having 1 to 23 carbon atoms, m is an integer of 1 to 10, and y is 0 or l). A composition for a polyolefin high foam consisting of seeds.

2. The composition according to claim 1, wherein the amount of volatile organic blowing agent is 5 to 80 parts by weight per 100 parts by weight of polyolefin.

3. The composition according to claim 1 or 2, wherein the total amount of the amine of the general formula fil and the amide of the general formula [0] is 0.05 to 15 parts by weight per 100 parts by weight of the polyolefin.

4. The composition according to claim 1, wherein the polyolefin is high density polyethylene.

5. The composition according to claim 4, wherein the high-density polyethylene has an HMI of 30 f/10 preparative t and a swell value of 3''/10 cm DJ.

6 Claims 1, 2, 3, 4, or 5, wherein the volatile organic blowing agent is a mixed blowing agent consisting of dichlorotetrafluoroethane and other halogenated hydrocarbons. Compositions as described.

7 The mixing ratio of dichlorotetranoroloethane and other halogenated hydrocarbons is l:4 to 4 in molar ratio.
:1.

8. Claim 6, wherein the halogenated hydrocarbon is at least one selected from trichloromonofluoromethane, dichloromonofluoromethane, dichlorodifluoromethane, l-dichlorotrifluoroethane, methyl chloride, and dichloridemethane. 7. The composition according to item 7.

Procedural Amendment 11'□1゛1 Cut/1981 Patent Application No. 92371 2 Issued January Horn Name (f1 Composition for Polyolefin Highly Foamed Material 3 1 Mountain 1) 4 Name/l1fl: 1 Applicant for license If Toha 1-2-6 Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture Representative Teru Miyazaki 1st generation 1111 people〒If14 Higashis;O, middle of the day! ] Sugin Kano 1i1'11
．． No. 5 I-ya [-: 11': + floor 711101
Kazukiya Column 8 of the detailed explanation of the invention in the specification, contents of amendment (1) "Volatile organic blowing agent" column on page 22 of the specification
1.2-dichlorotetrafluoroethane" and rl, 1
．． 2-) "Lichlorotrifluoroethane" was changed to "dichlorotetrafluoroethane" and "trichlorotrifluoroethane" respectively.
111・1' (Nonono+1 Patent Application No. 92371 of 1981, C"i">', l'l Composition for polyolefin highly foamed material) 1 mountain 11; 1 l:I Akane 1.1"1悄(+Patent applicant 1i1i1j 1-2-6 Dojimahama, Kita-ku, Osaka, Osaka Prefecture
Representative Teru Miyazaki 111/.

1) 11111 days/1Y1st power 111J Contents of spontaneous 8 correction (1) 1-Foaming rate in the bottom two lines of page 4 of the specification,
Corrected to 1 foaming ratio.

(2) On page 14, lines 5-4 from the bottom, correct []-trichlorotrifluoromethane lk, l'trichlorotrifluoroethane 1.

(3) In the table on page 24, the name in the column with the abbreviation ■ [N
-2-Hydroxyhexanamide-1 was corrected to 1+<-2-hydroxyethylhexanamide.

(4) [B114 and [Unlike'11] on page 37, line 5
31, [Corrected to B114 and R113-1.

(5) 1-Fx14 on page 39, lines 13 to 1.4
and Fl, 1. jli, “Corrected to 1-1114 and R113J-T.

(6) The following has been corrected in page 44, page 9, below.

Table 9 (force) l”F 11.4 and Fl on page 45, line 5
Corrected to ljl gold, l7) (114 and R113).

Claims (1)

[Claims] 1. (a) polyolefin/, (b) volatile organic blowing agent,
(c) At least one amine represented by the general formula % (1) or an integer of 1 to 2) and (11) (R2 in the formula has 1 to 5 carbon atoms) (R3 is a hydrocarbon group having 1 to 23 carbon atoms, m is an integer of I to 10, and y is 0 or 1) thing. 2 The amount of volatile organic blowing agent is 1% in 100 polyolefins.
The composition according to claim 1, which has a weight of 95 to 80 parts by weight. :t The amount of amine of general formula (1) and amide of general formula (I) is 0.05 to 100 parts by weight of polyolefin.
A composition according to claim 1 or claim 2, wherein the amount is 15 parts by weight. -1 The composition according to claim 1, wherein the polyolefin is high-density polyethylene. 5. The composition according to claim 4, wherein the high-density polyethylene has a HM work of 3 oy/1 o min or less and a swell value of 30 f/1 o crn or less. 6 Claims 1 and 21) i1 in which the volatile organic blowing agent is a mixed blowing agent consisting of 1,2-dichlorotetrafluoroethane and other non-logenated hydrocarbons.
% The composition according to item 3, item 1 or item 5. 7 The mixing ratio of I,2-dichlorotetrafluoroethane and other logenated hydrocarbons is 1:1 in molar ratio
7. The composition according to claim 6, wherein: 1. 8 The halogenated hydrocarbon is at least one selected from trichloroheptanofluoromethane, dichloromonofluoromethane, dichlorodifluoromethane, 1,1.2-)lichlorotrifluoroethane, methyl chloride, and dichloridemethane. Composition 0 according to claim 6 or 7, which is a species