JPS59189134A - Novel foam and production thereof - Google Patents

Abstract

PURPOSE:To obtain a foam having a uniform cell structure, excellent mechanical characteristics, heat resistance, etc., by blending a specified expansion retarder and a nucleating agent with high-density, high-melting, non-crosslinked polyethylene, adding a volatile org. blowing agent thereto, and expanding the compsn. CONSTITUTION:0.05-10pts.wt. expansion retarder capable of prolonging foaming time for at least one sec as compared with the case of no addition as measured by a glass tube expansion test method, e.g., 2-hydroxyethylamine and 0.001- 5pts.wt. nucleating agent such as talc are blended with 100pts.wt. non-crosslinked polyethylene having a density of 0.935g/cm<3> or above and a m.p. of 117 deg.C or above. A volatile org. blowing agent such as dichlorotetrafluoroethane is added to the resulting comsn. and the resulting mixture is expanded to obtain a foam which is composed of cloed cells having an average cell size of 0.05-3mm. and a density of 0.007-0.1g/cm<3> and in which fluctuation in the thickness of cell membrane is within + or -30% and coefficient of variation of cell size is within 70%.

Description

[Detailed Description of the Invention] This invention relates to a novel foam with excellent mechanical properties and heat resistance, and a good appearance. In addition to having an appearance of 2, it also has mechanical properties and heat resistance that were previously unobtainable.
Density 0.9 with high reliability over a long period of time
This invention relates to a high-performance foam made of substantially non-crosslinked polyethylene (hereinafter referred to as high-density polyethylene) with a weight of 5 g/cd or more and a melting point of 117°C or more.

So far, foams on the market include flexible polyurethane foam, hard polyurethane foam, crosslinked low-density polyethylene and non-crosslinked low-density polyethylene resin foam, polypropylene resin foam, and combinations of high-density polyethylene resin and ionomer resin. Mixed resin foams have been proposed, but none of these foams have been able to provide both mechanical properties and heat resistance, and are not necessarily satisfactory.

For example, although the above-mentioned soft polyurethane foam and hard polyurethane foam have excellent heat resistance, they have poor mechanical properties, and cross-linked low-density polyethylene resin foam has poor both mechanical properties and heat resistance, and non-cross-linked Low-density polyethylene resin foams have the disadvantage of being even more inferior in heat resistance than cross-linked low-density polyethylene resin foams. First, although polypropylene resin foam has excellent heat resistance, it has poor mechanical properties, while mixed resin foam of high-density polyethylene resin and ionomer resin has excellent mechanical properties but has poor heat resistance. It has the disadvantage of being inferior.

For example, until now, for high-density polyethylene foam,
Has it been proposed to blend and modify ionomers, polystyrene, low-density polyethylene, partially cross-linked rubber, etc.?
-40] Publication No. 66, JP-A-54-33569,
(Japanese Unexamined Patent Publication No. 54-161671), since a large amount of resin is required to be blended to achieve the desired effect, heat resistance inevitably deteriorates.

In addition, a superheated bath solution of a polymer sealed at high pressure in a pressure vessel and exposed to an active surrounding solution was heated under Harusada's concentration and temperature conditions.
By extruding into a low pressure area in a short time of 10 seconds or less,
It is also known to flash-evaporate the activated chemical composition to form a foam consisting of a large number of +7) cells, and at the same time rapidly cool it to fix the cell structure.It is also known to obtain a high-quality high-density polyethylene foam by the so-called flash extrusion method. (U.S. Pat. No. 3,227,784). However, in order to form a homogeneous foam through rapid foaming and cooling,
The extrusion speed must be increased significantly, and
It is not possible to foam the foam under extremely narrow tolerance conditions, which may cause wrinkles and unevenness on the surface of the foam, making it difficult to obtain a product with a good external appearance. It has the disadvantage of being unsuitable for manufacturing.

Further, as an improvement of this flash extrusion method, a method is known in which the cell diameter 'i is increased to 500 μm or more in order to improve the tear strength (US Pat. No. 3,787,543).

However, in order to form large cells in this method, it is necessary to limit the number of bubbles generated during extrusion. Therefore, it is necessary to avoid as much as possible the presence of not only the normally added nucleating agents but also the presence of substances that increase the number of air bubbles such as dust and gel particles that are accidentally introduced. Without using a nucleating agent, it is not possible to obtain a uniform cell diameter and cell film thickness.
In addition to the inevitable reduction in compression recovery rate and the occurrence of wrinkles and unevenness on the surface of the foam, there are also disadvantages in that it is impossible to obtain a foam with a thickness that is more than opaque.

Furthermore, as a blowing agent in the molten polyethylene,
A method has also been proposed in which 1.2-dichlorotetrafluoroethane is added under pressure, stored at high pressure in a pressure-resistant container, and rapidly extruded into the atmosphere to cause expansion and foaming (U.S. Patent No. 3). 067.147), it is difficult to obtain a foam with good mechanical strength and surface condition because it is forced to foam a material with low melt viscoelasticity.

In addition, when foaming high-density, high-crystalline polyethylene, it is recommended to add a heat sink, such as an alkanol having 2 to 5 carbon atoms, to the molten polyethylene along with a foaming agent, so that the solidification of the polyethylene follows the generation of expansion gas during the foaming process. Has a method been proposed to prevent the latter from escaping and form a good foam (U.S. Pat. No. 3,102)?
, No. 865], in this method, rapid foaming,
Since rapid cooling is required, it is difficult to obtain a foam that has excellent mechanical strength and a good surface condition, similar to the method described above.

On the other hand, when high-temperature compositions made of polyethylene containing a foaming agent are extruded from the die of an extruder, they are drawn at a drawing line speed lower than the extrusion line speed of unfoamed compositions, and while gradually cooling, 50% of the total bubbles are removed. A method has also been proposed in which a hard foam with high compressive strength is obtained by growing the foam to a diameter of 5 mm or more (Japanese Publication No. 57-22741), but the foam obtained in this way is Most of the physical properties such as cushioning properties, compression recovery properties, and heat insulation properties are insufficient, and it cannot be said to be practically satisfactory.

In this way, high-density polyethylene, which has a high melting point (high degree of crystallinity), has a larger viscoelastic change near the melting point suitable for foaming than low-density polyethylene, so the range of suitable foaming temperatures is significantly limited. In addition, the crystallization heat generated during foaming and other factors interact in a complex manner, making it difficult to maintain proper foaming conditions, making it easy for the surface of the foam to become rough and quality to deteriorate due to the destruction of bubbles. In addition, low-density polyethylene has long chain branches and high melt viscoelasticity, whereas high-density polyethylene does not have long chain branches and has low bath melt viscoelasticity. When performing foam molding by opening from a high pressure region to a low temperature and low pressure region, it is difficult for uniform cell expansion to occur, resulting in deterioration of physical properties due to cell rupture.
Easy to cause appearance defects such as poor moldability. For example, in extrusion foaming, when extruding from a die into a low-temperature, low-pressure region for foaming, it is not possible to suppress the generation of bubbles in the die, and the bubbles already generated in the die are wrapped up in the extruded amount. In the process, it is destroyed by heat and shear forces, resulting in poor quality of the foam. This tendency tends to be more pronounced as the cross-sectional area of the die opening increases, that is, as the thickness of the foam increases. To solve this problem, it may be possible to dramatically increase the extrusion rate or to place the molten resin containing a blowing agent in a closed container and instantly open the container. However, since the foaming speed is extremely high, a significantly large amount of extrusion is required to completely eliminate the negative effects of bubble generation in the die. Must be. Furthermore, if the extrusion rate is excessively increased, flow disturbances such as melt fractures occur, resulting in poor appearance such as unevenness and uneven thickness on the surface of the foam. - Even in the method of instantaneously opening a sealed container, it is not only difficult to provide an opening speed sufficient to correspond to the foaming speed, but also to obtain a foam with good appearance such as surface condition and moldability. It is difficult.

Therefore, various proposals have been made so far, lt”i(t
Despite this, what has actually been put into practical use is
Made of low-density polyethylene or polypropylene foam or giant cell foam, it has a uniform, closed, fine cell structure.
High-density polyethylene foam, which has both excellent appearance and mechanical properties, has not yet been put to practical use.

In view of these circumstances, the inventors have conducted intensive research to develop a foam that has excellent appearance, mechanical properties, and heat resistance, and have found that a specific foaming moderator can be used. As a result, the inventors discovered how to achieve the object and came up with the present invention.

That is, non-invention is dense fl O, 93sy / C1
A foaming moderator 0 that extends the foaming time by 1 second or more compared to the case without additives and has a low capacity of 5% in the glass tube foaming test method for 100 parts by weight of substantially non-crosslinked polyethylene with a melting point of 117°C or higher and a melting point of 117°C or higher. A composition containing 0.05 to 10 parts by weight and optionally 0.001 to 5 parts by weight of a nucleating agent is obtained by foaming. 0,007~0-10&/cn
i. A 1-fila foam is provided, characterized in that the variation in the thickness of the cell membrane is within ±30 factors, and the coefficient of variation of the cell diameter is within 70 factors.

In other words, by including a foaming moderator, the foaming speed, which is extremely high in non-removed skin, is slowed down, and the generation of bubbles at the initial stage of foaming is suppressed, resulting in less tearing of the cell walls, excellent mechanical properties and heat resistance, and a high appearance. It is possible to obtain a beautiful foam.

Here, the foaming moderator is defined by the glass tube foaming test method.
In the foaming phenomenon in which a biocomposition is released from a high temperature and high pressure region to a low temperature and low pressure region, this method serves as a representative indicator of the behavior and is easy to observe.

In this glass tube foaming test method, by adding an additive that has the ability to extend the foaming time compared to when no foaming moderator is added, a foam with superior physical properties and appearance can be obtained. I found out that Rokoto.

This glass tube test method is carried out as follows.

In other words, as shown in Fig. 1, the internal volume is 16 cc (inner diameter 1
A resin or resin mixture used for the actual foam (a predetermined amount of additive 7J[ ] 7\IJ ke) is placed in a transparent pressure-resistant glass tube 1 with one end closed (2 mm φ, 140 mm long) in polyethylene. After kneading, powder or pelletized) 2.4. O
g, and after reducing the pressure to about 10 ranH9, dichlorotetrafluoroethane 1.03. ! Inject 9 and trichlorotrifluoroethane and close ball valve 4 to seal the tank. Next, the glass tube 1 is immersed in a room-temperature glass oil bath 5 as shown in Figure 2, and then placed in the oil bath and heated to 40°C. 14
Hold at 0° C. for about 1 hour to impregnate the blowing agent into the resin or resin mixture to form a homogeneous, transparent molten mixture 3. If the resin already contains other additives and the molten mixture does not become transparent, conduct the test using the resin without the additives. After that, observe changes in the transparent molten mixture 3 while lowering the oil temperature at a cooling rate of 0.75±0.1"C7 minutes. Before long, swirls begin to appear in the transparent molten mixture 3. When the oil temperature reaches 0.5℃ below that temperature, the ball valve 4 is rapidly opened.
Observe the state of the molten material 3 in the glass tube 1 at the same time as the pressure in the glass tube 1 is lowered to atmospheric pressure. As I was observing, I noticed that the molten mixture in the glass tube was fine 3I7 old C? A capsule forms and then begins to foam, filling the glass tube and causing further expansion. The cylindrical material does not come out of the glass tube until the foaming is completed.

The time from the opening of the valve until the end of foaming is measured and is referred to as the "foaming time".Table 1 shows the results of experiments conducted in 5 using various combinations of additives for the resin.Data are all average values of five measurements.The additives used in this experiment are shown in Tables 2 to 4.1-0 In Table 1, the experiment NIL 31.32 does not contain additive 7JO agent. , N range 1 to 30 contains additives. Some additives shorten the foaming time, while others lengthen it. Foaming time - 1 second or more compared to when no resin is added. Foam moderators that lengthen the foam are suitable as non-inventive foam moderators.

Most of the composition of the material constituting the cell walls of the non-inventive cells is substantially non-crosslinked polyethylene with a density of 0.935 g/cc or more and a melting point of 117°C or more, and a part of it is mixed with a foaming moderator. In some cases, a nucleating agent is further mixed in a portion.

Polyethylene must be virtually non-crosslinked; crosslinking can cause the cell walls to become brittle, which is a characteristic of polyethylene.
7) It is not preferable because it causes loss of flexibility and decreases physical properties such as tensile specific strength.

In addition, this polyethylene needs to have a density of 0.935 g/CC or more and a melting point of 117°C or more, and 0.93
Those with a melting point of less than 5 g/cn1 do not provide sufficient tensile specific strength, and those with a melting point of less than 117''C do not provide a sufficiently low heat shrinkage rate.

The polyethylene used in the invention has a density of 0.935.9
/cn1 or higher and a melting point of 117°C or higher, which is a polymer mainly composed of ethylene, and includes not only ethylene homopolymers but also ethylene and other polymers such as propylene, 1-butene, 1-hexene, 2-natylpentene, etc. It may also be a copolymer with a monomer of Also, is that the 30 weight person? As a limit, it may contain other resins or rubbers, or it may contain a commonly used additive 7JIJ agent.

As the polyethylene used in the invention, 190°,
Load g21.6 to 9 melt index (HLM
engineering) is 0.02 to 40. ! Particularly suitable are those with a swell value of 20 to 50 fj/20 on. This melt index is 0.02g/l
If it is less than 0 minutes, the molding condition (surface smoothness, shape stability)
(If it is larger than 40g710 minutes, the Wttr property will be poor and it is not preferable.The swell value is 20.9720 cm
If it is smaller, the foaming condition will be poor, so 50 g 720
If it is thicker than cm, the molding condition (surface smoothness, shape stability)
This is not preferable because it worsens the condition.

The foaming moderator, which is another component constituting the membrane wall, is mixed with the polyethylene for the reasons mentioned above, and the foaming rate is lower than when it is not added in the glass tube foaming test method. It is preferable that the melting time be extended for 1 second or more, preferably 2 seconds or more, and that the melting point is lower than the melting point of the polyethylene, and that it can be uniformly mixed into the bath-melted polyethylene.

Suitable foaming moderators include the general formula % (1) (where R is a fullylene group having 1 to 5 carbon atoms, A is a hydrogen atom or an acyl group, and n is 1 to 10 integer, X is O or 1
- 2) or the general formula % (in the formula, each R2 is a divalent hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different from each other, m is an integer of 1 or more) Or, the general formula R11 is a hydrocarbon group having 1 to 6 carbon atoms, and l is 0 or 1 to 6
R6 and R are hydrogen or a hydrocarbon group having 1 to 23 carbon atoms, and R8 is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. ] Can you name a compound?

In the present invention, the general formula t is used as a foaming moderator.
Examples of the compounds shown in l) include 2-hydroxyethylamine, di-2-hydroxyethylamine, tri-2-hydroxyethylamine, 2-hydroxypropylamine, di-2-hydroxyglopylamine, tri-2-hydroxypropyl amine, 3-hydroxypropylamine, di-3-hydroxypropylamine, tri-3-hydroxypropylamine, tri-polyoxyethyleneamine, and ester compounds of these with fatty acids, such as tri-2-hydroxyethylamine monostearate, tri-2- Hydroxyethylamine distear-1
, tri-2-hydroxyethylamine) IJ Stearley), 1-IJ-2-hydroxyethylamine silaurylate, tri-2-hydroxyethylamine silaurylate, and tri-2-hydroxyethylamine trilaurate. Particularly preferred are
These include 2-hydroxyethylamine, di-2-hydroxyethylamine, tri-2-hydroxyethylamine, 2-hydroxypropylamine, di-2-hydroxypropylamine, and tri-2-hydroxypropylamine. These amines may be used alone or in combination of two or more.

Examples of compounds represented by the general formula (Il+) include ethylene glycol, fropanediol, butanedimer, bentanediol, hegyzanediol, polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, and polyoxyethylene polyoxypropylene glycol. Particularly preferred are polymers having the general formula % (in the formula, R3 and R4 are hydrocarbon groups having 1 to 6 carbon atoms, and R3 and R4 are different hydrocarbons). a, b.

C is an integer of 1 or more.
4 is a polyoxyethylene polyoxypropylene block polymer of CH3-CH-CH2-.

Examples of compounds represented by the general formula +1> include betaine, laurylbetaine, stearylbetaine, laurylglycine, stearylglycine, lauryldi(aminoethyl)glycine, and stearyldi(aminoethylglycine).
, glycine, alanine, valine, leucine, etc. Particularly preferred compounds are lauryl betaine, stearyl betaine, lauryl di(aminoethyl)glycine, and stearyl di(minoethyl)glycine.

These compounds may be used alone or in combination of two or more. It can also be used in combination with other σ) additives.

The mixing ratio of these foaming moderators should be selected within the range of 0.05 to 10 parts by weight, preferably 0.1 to 8 parts by weight, based on 100 parts by weight of polyethylene.

If this amount is less than 0.05 part by weight, the effect of slowing down the foaming speed will not be sufficient, and the appearance of the obtained foam will deteriorate and the mechanical properties will deteriorate. Moreover, if the amount is more than 10 parts by weight, no great effect can be expected considering the amount blended, and furthermore, the strength of the polyethylene constituting the cell walls is reduced, which is not preferable.

Furthermore, it is a feature of the invention that ~5 parts by weight of a nucleating agent o, ooi to 100 parts by weight of polyethylene is added to the foaming mixture, and this eliminates the conventional technology (for example, U.S. Pat.
, 787,543, a foam with a uniform cell diameter and a high closed cell ratio (that is, a high compression recovery system) was obtained. As the nucleating agent, any conventionally used nucleating agent may be used. Examples of such materials include fine inorganic powders such as clay, talc, and silica, and fatty acid metal salts such as zinc stearate and calcium stearate. Further, it may be something that decomposes during foaming and cannot be detected in the foam, or it may be a finely powdered pigment or the like.

If the amount of the nucleating agent exceeds 5 parts by weight (4), the appearance and mobility will deteriorate, which is not preferable.

The inventive foam consists of closed cells with an average cell diameter of 0.05 to 3 mm, preferably 0.1 to 2 mm, and a foam density of 0.007 to 0,10,! 710/I, preferably sails 0 to Q, 05g/c! It is necessary that the foaming be carried out so that the variation in the thickness of the bubbles is within ±30 coefficients, preferably ±2525 coefficients, and the coefficient of variation of the bubble diameter is within 70 coefficients, and outside this range 2) However, the tensile specific strength, compression recovery rate, heat shrinkage rate, and appearance are unsatisfactory.

Closed cell means that the open cell ratio is 20 parts or less as measured by the air pyranometer method as shown in ASTM D-2856, and compression recovery is required when the open cell ratio exceeds 20 parts. Physical properties such as ratio decrease. A preferable open cell ratio value is 10% or less.

The non-inventive foam is made of a specific polyethylene containing the above-mentioned foaming accelerator, and has a uniform cell structure that is independent and has a small variation in cell membrane thickness and a small coefficient of variation in cell diameter. tensile specific strength 150Kg/cr1
As described above, we were able to achieve excellent physical properties such as a compression recovery rate of 80 coefficients or more, a cutter edge heat shrinkage rate of 50 coefficients or less, a thickness unevenness of less than 50 coefficients, a corrugation value of less than 50 coefficients, and a surface smoothness of less than 2 coefficients. .

When the birefringence of the foam membrane of the inventive foam is observed under crossed Nicols using a polarizing microscope, at the extinction position, as shown in Figure 3a, a point with a diameter of approximately 5 μm or less is observed in the dark. It looks like a 5-shaped image that has been scattered evenly.

This is thought to be because the non-inventive foam contains a second foaming agent, which expands slowly and uniformly as air bubbles are formed. reactor. On the other hand, commercially available polypropylene foams that are exposed to rapid expansion/8 appear dark all over, as shown in Figure 3.

Although the inventive foam can be produced by known methods, extrusion foaming is preferably used.

According to the uninvented method, (a) density 0.935 E/
/ad or higher, substantially non-crosslinked σ polyethylene with a melting point of 117°C or higher, (b) 100 parts by weight of polyethylene, (b) a foaming retarder with a foaming time of more than 100 seconds and a 5-filtration capacity compared to a non-additive foam test method according to the glass tube foaming test method. agent 0.05 to 10 parts by weight, ?・) 0.001 to 5 parts by weight of adhesive and (d) volatile organic blowing agent 3
0 to 140 parts by weight of the polyethylene is heated under high pressure at a temperature higher than the melting point of the polyethylene, and extruded from a high temperature and high pressure area to a low temperature and low pressure area for continuous foaming, thereby obtaining the desired foam. .

To best carry out this method, 100 parts by weight of a specific polyethylene and a specific foaming moderator are heated to a sufficiently high temperature of 0.05 to 1°C to melt the polyethylene and knead the mixture well. and apply sufficient pressure. 1 to 14 oz of volatile organic blowing agent is injected into this molten mixture through an injection port provided at the tip of the extruder at a pressure sufficiently higher than the internal pressure of the extruder, and the mixture is thoroughly kneaded to uniformly distribute the volatile organic blowing agent into π. Disperse it. This mixture is cooled to a temperature slightly higher than the melting point of polyethylene (20° C. at most) using a cooling device connected to the extruder, and extruded through a die into a low temperature, low pressure machine. At this time, whether the mixed composition containing the volatile organic blowing agent foams or not, the foaming moderator suppresses the formation of σ bubbles in the die, and the foaming begins a short distance after exiting the die. The process begins to produce a soaked foam with good surface appearance and mechanical properties.

The polyethylene used here has a density of 0.935g/cc
As described above, it is substantially non-crosslinked polyethylene with a melting point of 117" C1 or more, and the foaming moderator is used in the glass tube foaming test method to increase the foaming time to 2 seconds or more, preferably 2 seconds or more, compared to the case without additive. It is an extended vine compound, more preferably one or more compounds represented by the general formulas (1) to 1it).

Note that the blowing agent used in the present invention is a volatile organic blowing agent, and by using this, it is not possible to obtain a foam with a high ratio from non-crosslinked polyethylene using a method that mainly uses non-crosslinking. [“Plastic Form Handbook I (Maki, Hen Osakata, published by Nikkan Kogyo Shimbunsha), No. 119-1
20 pages].

As the volatile organic blowing agent, halogenated hydrocarbons are preferable, and different types of halogenated hydrocarbons are used. 17 doubling yarn is more preferable. Preferred examples include mixed blowing agents consisting of dichlorotetrafluoroethane and other halogenated hydrocarbons, and particularly preferred among the halogenated hydrocarbons are trichloromonofluoromethane, dichloromonofluoromethane, and dichloromonofluoromethane. At least one selected from fluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, methyl chloride, and dichloride methane.In this mixed blowing agent, dichlorotetrafluoroethane and other halogenated carbonized The mixing ratio with hydrogen is preferably in the range of 1:4 to 4:1 in terms of molar ratio.
It is preferably in the range of 3:3 to 7:3.

In the present invention, the mixing ratio of the volatile organic blowing agent is preferably in the range of 10 to 140 parts by weight, more preferably in the range of 20 to 70 parts by weight, and less than 10 parts by weight. It is difficult to obtain a highly foamed product, and even if the mixing amount is increased to 140 parts by weight, the foaming ratio does not increase much and it is uneconomical, and furthermore, the quality of the foam deteriorates. So I don't like it.

In addition, in the case of non-invention, feed f7 to the extruder;) Additives commonly used in polyethylene mixtures, such as lubricants such as zinc nateate, ultraviolet absorbers, antistatic agents, stabilizers, colorants, You can add flame retardants, etc.

The non-inventive foam is a closed-cell foam with excellent heat insulation and cushioning properties, making it very useful for insulation materials, packaging materials, and the like.

Next, the invention will be explained in more detail with reference to examples, and the physical property values shown in each example were measured as follows.

/ \ / (1) Density of polyethylene Polyethylene (comparative commercial products are made by cutting out cell walls constituting cells from foam) at a temperature of 20 ± 2
After being maintained at a temperature of 65±5% at a relative humidity of 65±5% for 12 hours, the sample was placed in a n-butanol-triethylene glycol density gradient tube prepared according to JIS K6760 at 23°C, and its density was measured. There are three test pieces,
The average value is shown as .

(2) Melting point of polyethylene The peak humidity of the melting curve of polyethylene (comparative commercial products are obtained by cutting out the cell walls constituting the cells from the foam) using a differential scanning calorimeter (D, S, C,) is the melting point. The measurement conditions are as follows.

Zamble weight: 7 mq Scan speed = 16 ° C / mln (3) Polyethylene swell 1 round 1 Polyethylene (For commercial products as comparative examples, foam
After compressing with a press at 50℃, finely pulverize the powder to a diameter of 50 mmφ (silicone length/Norindaro diameter -30
) Supply to the extruder 6. A circular die with an inner diameter of 10 mmφ and an outer diameter of 16 mmφ is installed downward at the tip of the extruder, and the screw rotation speed is 46 rpm and the temperature is 18 mm.
A tube-shaped molded product is extruded at 0°C, the naube is quickly cut out 20 nm below the die surface, the weight of the tube with a length of 20 crn immediately after extrusion is measured, and the value is calculated as the swell 11 section (unit: ?/ 20crn). , (4) Polyethylene melt intex polyethylene (for the commercial product of comparative example, the cell wall constituting the air bubbles was cut out from the J1 body) was prepared according to JISK676.
0 according to 6i11'i/ko.

/ Kodashi 41] The constant temperature was 190°C, but the constant temperature for d was changed to 21.6 kg.

5) Measure the average cell diameter of the foam and the coefficient of variation of the cell diameter at the next bag distribution using a magnifying knife if necessary. Three cubes with one side of LO mm or more are arbitrarily cut out from the foam sample. However, if the thickness is less than 10 sn, it may be a rectangular parallelepiped. On one side of the cut cube, measure the longest length of each bubble in any one direction.

The measurement shall be performed on at least 10 bubbles in one direction. Next, similar measurements are made in a direction perpendicular to this direction. Measurements are made on three orthogonal cubes
Do this for two aspects. Let the arithmetic mean value of the measured values for the three cubes be the average bubble diameter.

The standard deviation is calculated from the measured value of the bubble diameter obtained as above, and then the coefficient of variation of the bubble diameter is calculated according to the following formula:
This is used as an evaluation scale for the variation in bubble diameter.

When the coefficient of variation of the air color frame exceeds 70%, the non-uniformity of the bubble diameter becomes noticeable and the quadruple value becomes noticeably inferior. Preferably 4
Set it at 0% or less.

(6) Variation in the thickness of the cell membrane of the foam The thickness of the cell membrane is determined by directly observing the cross section with a microscope, or by taking a photomicrograph and measuring from the photo, as described below.

1. Cut out a cube with a side of 10+ nm or more from a foam sample using a razor blade. However, the thickness is ], Omm
In the case of -F, a rectangular parallelepiped may be used. On a plane parallel to one cross section of the cut cube, use a razor blade to cut 0.
Cut out sections with a thickness of 5 to 1 mm. At this time, the cube may be cut into a size that makes it easy to cut out sections. The cut sections were observed under a microscope to measure the thickness of the bubbles. If the film is thin (less than 1 μm), the gold is evaporated onto the sample surface using a vacuum evaporation device, and then observed and measured using a scanning electron microscope. The measurement was performed at five points dividing the intersection of the bubble membrane into six equal parts for one bubble membrane, and the uniform membrane (X),
uill to find the maximum film thickness (X,) and minimum film thickness (xz)
When determining, the magnification should be such that it can remove stains of at least two significant figures. (For example, 300 if the film thickness is 10 to 20μ
Measurement is performed on any three or more bubble membranes belonging to different bubbles in one direction, and the same measurement is repeated in three orthogonal directions.

For each cell wall, Xi −x/ x x 100
(%) and XX2/X X 100 (%) to evaluate the variation in film thickness. When the thickness variation of all the measured bubble membranes is within ±30%, it is assumed that the thickness of the bubble membrane is uniform. Preferably it is within ±25%.

(7) Departure? Birefringence test of the bubble membrane of the envelope From the foam sample, in the same way as the measurement of the thickness of the bubble membrane,
Cut out a piece of bubble membrane with a razor blade. .

For samples with large bubble diameters, the thickness is 0, 5 + nm.
Cut out the section below, and in the section, either one of the bubble membranes or hbr
For samples with small bubble diameters of 3°, for which it is sufficient to observe the part almost parallel to the blood, the specimen may be immersed in a surfactant water bath, frozen, and then cut.

The low refraction test is performed by observing a section containing a cut-out bubble film or a single bubble under a polarizing microscope under crossed Nicols. 1 when the sample is rotated under crossed Nicols and the extinction position is reached.
Observe elephants.

An elephant to be glared at can be roughly divided into: (a) When the air/@) ventilation surface appears dark as shown in Figure 3b, (r+) When there is an elephant with a diameter of 5 μ or more in the darkness as shown in Figure 3a. If numerous circular or elliptical smoke spots (parts of different colors) appear, or if spots with dimensions exceeding 5μ are visible, (→ Part of the bubble film may appear to change color.) .

It is appropriate to perform these observations using a single valence light microscope at a magnification of about 700 times.If it looks like Q (=) and ni), the bubbles are expanding non-uniformly and the physical properties have deteriorated. cause In contrast, in the cases shown in Figures 3a, 3b, and 3b, it is considered that the expansion is uniform.

(7) Density and specific gravity of foam A test piece with a volume of 50 centimeters or more is used, and the weight is weighed to the nearest ±1 centimeter. Next, the test piece was immersed in a knife/linda filled with water to about half the volume, and the body g of the test piece was measured with an accuracy of ±1% from the rising sieve of the water '+16. , calculate the foam density D(f/ari) of the test piece using the following formula. .

D = -- ■ Where W: Weight of the test piece (7) V: Volume of the test piece (c2y) The test piece was kept at a temperature of 2°C ± 2°C and a relative humidity of 65°C before the start of the test.
591; kept at a temperature and humidity for 12 hours or more, the number of test pieces was three, and the average value was determined.

In addition, the foam density is the total density of water at 4°C (12Zcrd
) to determine the specific gravity of the foam. This value is used to determine the tensile specific strength of the foam.

(8) Tensile specific strength test piece of foam is long 8011111, width 10 + nm, thickness 5
It is assumed that the threshold rectangular parallelepiped is maintained at a temperature of 20° C. and a relative humidity of 65±5% for 12 hours or more. If the sample has anisotropy, specimens shall be taken in both the vertical and horizontal directions.

If the thickness of the foam sample is less than 5 cm, take a test piece at the same thickness.

For tensile test cracking, use a device that has a maximum load indicator and the maximum load during the test is in the range of 5 to 85% of its capacity. Tolerance of relative movement speed of specimen grip is ±5
%, and the male tolerance of the unloading scale is 12%. The test piece was placed in the grips at the right angle 1' (M) to avoid distortion or other inconveniences during the test, the distance between the grips was 50 mm, and the test was carried out at a tensile speed of 500 mm/mrn. Pull the piece and measure its maximum weight.Then, find the tensile strength (9/cn1) using the following formula.

1+1 where F: Maximum load at the point of cutting (K2) W: Width of the test piece (, n) t: Thickness of the test piece, etc. Next, the obtained tensile strength is calculated as the value of the foam sample. Divide by the specific gravity to find the tensile specific strength. The number of specimens for test 1 shall be 5 (if the sample has anisotropy, use the specimen collection button) to the extent possible.
(5 pieces each in the longitudinal, longitudinal, and thickness directions), and the result is an average of 11% for all of them, which is 7%.

(9) Compression recovery rate of foam The test piece has a length of 100 +tan, a width of 40 mm, and a thickness of 50 mm.
A simple rectangular parallelepiped was kept at a temperature of 20±2° C. and a relative humidity of 65±5% for 12 hours.

If the thickness of the foam sample is less than 50mm, overlap them to make 50mm. Use a compression testing machine capable of constant speed compression, compress the specimen to 50% of its initial thickness at a compression speed of 10 mjn/#+In, immediately remove the load,
Leave it for 30 seconds, wait for the thickness to recover, and then perform a second 50% compression test in the same manner on the recovered thickness. This operation is repeated five times in total, and the recovered thickness after the fifth compression is measured. Then, calculate the compression recovery rate using the following formula.

1 Compression enclosing rate (%) = -X100 2 Here tl: initial thickness (c,,) t2: Recovery thickness after 5 compressions (b) The number of test pieces is 3, and the average value is shown.

The heat shrinkage test piece for σO foam was a cube with a length of 40mm, a width of 40y++m, and a thickness of 5cm, and was kept at a temperature of 20±2℃ and a relative temperature of 65±5% for more than 12 hours. 6. If the thickness of the foam sample is less than 5Tmn, take a test piece with the same thickness. Using a hot air circulation dryer with a temperature control accuracy of 13.0±2°C, the test piece was placed horizontally in the hot air circulation dryer maintained at 1:30°C and heated for 5 hours. Take out the test piece and leave it in the test place under standard conditions for 1 hour, then calculate the volume of the test piece and use it as the volume after heating. The volume is determined by submerging the test piece in water in a graduated cylinder approximately half filled with water, and determining the height of the rise of the water surface. And 130℃ according to the following formula
Figure out the heating shrinkage rate (%).

O Here Vo: Initial body M (clll) ■l: l: Heating volume (clll) Three test pieces were used, and the average value is shown.

(11) Appearance of the foam (1) Thickness unevenness of the foam To measure the thickness unevenness of the foam, in the case of a sheet or board, cut the foam in a plane perpendicular to the extrusion direction, and measure the width from the edge of the foam. ], find the maximum value (1+) and minimum value (t2) of the thickness of the portion excluding the portion corresponding to 0%. The thickness unevenness is determined by the following formula.

1.12 Thickness unevenness--X 100 (%) 2 Measurements are taken at five locations on the cross section and the average is taken.

In the case of a columnar or cylindrical shape, cut the foam in a plane perpendicular to the extrusion direction, and measure the maximum diameter or thickness (1
, ) and the minimum value (t2), and calculate the above formula.

(11) Corrugation value of foam (see) and d: In the case of a board-shaped foam, cut the foam at m' perpendicular to the extrusion direction without trenching. At this time width 20
In the case of a sample crn or more, the length shall be measured at li'120cn+ or more, and if the width is less than 20 on, it shall be measured at the original size. This foam is placed on a flat surface without applying any force, and the distance from the flat surface to the upper surface of the foam is measured to determine the maximum distance (tt) and minimum distance (t2). At this time, a portion corresponding to 10% of the width from the end of the foam is removed. The collate value is determined by the following formula. Measurements are taken at five locations in the cross section and the average is taken.

/-112 Corrugation value - - Maximum distance (-g+) and minimum distance (
Find t2). The corrugation value can be calculated using the above formula.

(iii) Surface smoothness of the foam The surface smoothness of the sheet or boat-shaped foam wrapper is evaluated as follows. ] Cut out the pieces to a length and width of at least 30 cm, excluding the corresponding part. If the length and one piece is less than 38 on, W: M ml
The maximum length of sleep that can be taken excluding s and 1J.

Place the cut out package above 1,000 mJ without applying any force,
In the four cut planes, the distance from the plane to the foam wall is measured to determine the maximum distance (L).

In the case of a cylindrical or cylindrical foam, the foam is cut along a plane perpendicular to the extrusion direction and cut to a length of 30 or+ or more. If the length is less than 30W, it shall be the maximum length that can be obtained.

9. Place the cut foam on a flat surface without applying any force, observe the cross section of the foam from the side in the longitudinal direction, and determine the maximum distance (L) from the flat surface to the lower surface of the foam.

Measurements are made at four points at positions where the foam is rotated by 90 degrees. The maximum pressure m1l (L) of all measurements is taken as the surface smoothness.

Next, the definition of the rank of the appearance evaluation of the foam used in the examples shown below will be described.

(1) Thickness unevenness of the foam A: Thickness unevenness of less than 30% B: Thickness unevenness of 30% or more but less than 50% C: Thickness unevenness of 50% or more (2) Colcate value A Nicol of the foam Gate value is less than 50% B Nicol gate value is 50% or more and less than 1.00% C Nicol gate value is 100% or more (3) Surface smoothness of foam A: Surface smoothness is less than 1 mm B: Surface smoothness C: Surface smoothness is 2 or more (4) Comprehensive evaluation of foam appearance Comprehensive evaluation of foam appearance is performed according to the following criteria.

A Thickness unevenness, corrugated clay and Q surface flat i'1'! A foam that is A in all evaluation items.

Ruru foam with good appearance and excellent commercial value.

B A foam that contains one score of B and no score of C in any of the evaluation items of thickness unevenness, corkate value, and surface smoothness.

Although the appearance is slightly inferior, the foam is sufficient to match the product 111II clay.

If one song is rated C in any of the following items: thickness unevenness, corrugated value, and 4 i7o smoothness, it will be rejected.
Wrapping body.

The surface of the foam has noticeable unevenness, wrinkles, etc., and the foam has poor clarity.

Next, the present invention will be explained in detail by way of examples.

The resins and compounds used in Examples and Comparative Examples are shown in Tables 2 to 5.

Example 1 100 parts by weight of Santic B870 as a resin, 0.5 parts by weight of Pronone 2010.5 parts by weight as a foaming moderator, and 0.1 part by weight of Merck as a nucleating agent were triblended using a Henschel mixer, and then sufficiently uniformly kneaded using a mixed wire extruder. A base material for foam molding was prepared.

The base material for foam molding was heated to a maximum of 220°C with a diameter of 6.
The mixture was supplied to an extruder with a diameter of 5 columns at a rate of 40 kg/hr, and heated and mixed with the foaming agent press-fitted through the foaming agent injection port provided at the tip of the extrusion tube. As blowing agents, dichlorotetrafluoroethane and trichlorotrifluoroethane were used at 1.5
: A mixture with a molar ratio of 1.3 was used, and 50 parts by weight were continuously supplied using a high-pressure pump to 100 parts by weight of high-density polyethylene. The heated mixture was placed in an extruder and cooled to 126°C with a cooling device, and then continuously extruded into the atmosphere through a rectangular shape with an opening dimension of 35 mm wide and 2.2 mm thick to form a foam with a thickness of 15 mm and a width of 125 mm. A whole plate-shaped foam was obtained.

The properties of the obtained foams are shown in Table 6.1) The foams produced by '0# have a maximum variation in the thickness of the cell membrane of 22%.
It is a foam that has independent and uniform cell distribution, and has a good appearance, excellent mechanical properties, and heat control properties. In a birefringence test using a polarized light microscope on a bubble film, the type shown in Figure 3a, in which minute white dots appear dispersed, was found. , Comparative Examples 1 to 7 Table 6 shows the characteristics of various commercially available foams.

The types of each foam are as follows3. Comparative Example 1 Non-crosslinked low-density polyethylene foam Comparative Example 2 Non-crosslinked high-density polyethylene foam Comparative Example 3 Non-crosslinked polypropylene foam Comparative Example 4 High-density polyethylene Comparison example 5 of mixed resin resin foam of and ionomer Comparison of cross-linked low accumulation polyethylene foam? U6
Crosslinked Polypropylene Foam Comparative Example 7 Compared to the flexible urethane foam Example 1, the foams of Comparative Examples 1 to 7 were inferior in appearance, mechanical properties, and heat resistance.

Example 2 The types and amounts of resin and foaming moderator were as shown in Table 7, Experiment No. 1.
A foam was obtained in the same manner as in Example 1, except for the types and amounts shown in 6 to 6.

The customization of the resulting foams is shown in Table 7 @ numbers 1-9. Note that the resin and foaming moderator are the same as those for extrusion foaming, but the results of the foaming time in a glass tube foaming test for the composition excluding the nucleating agent are also shown.

The resulting foams had open cell ratios of 10% or less for Experimental Nail Nos. 1 to 8, and 18% for Yokoki No. 9, both of which had independent and uniform cells. The foam has a variation of less than ±30% in all cases, with a good appearance and an excellent score of 89. It had mechanical properties and heat dissipation properties of 11tfi. In the birefringence test of bubble membranes using a polarizing microscope, fine white dots appear dispersed.
It was the type shown in figure a.

Comparative Example 8 The resin was the resin shown in Table 7 Experiment Nos. 10 to 13,
A foam was obtained in the same manner as in Example 1, except that the foaming speeder was not added too much, or the additive shown in Table 7 Experiment 1 Experiment No. 12.13 was added instead of the foaming moderator. Ta.

The properties of the obtained foam are shown in Table 7, Experimental Nos. 10 to 13. The table also shows the results of the foaming time in a glass tube foaming test using the same resin and additives as in the extrusion foaming, but excluding the nucleating agent1. When additives with no deceleration effect were added, all foams had a cell structure with poor closed-cell properties and uniformity of cell diameter, and foamed materials with poor mechanical properties. It was the body.

Example 3 Santic B880 100 months i j
i: Starhome F as a foaming moderator for 14rls
:3, 0 parts by weight, talc 0.05 as core 1i11
using 80 parts by weight and an equimolar mixture of dichlorotetrafluoroethane and dichloride methane as a blowing agent,
A foam was obtained in the same manner as in Example 1.

The obtained foam has a uniform and closed cell structure, the variation in the thickness of the cell membrane is within ±30%, the foam density is 0.0107 q/atl, the average cell diameter is 0.52, and the cell size is Coefficient of variation in diameter 48%, tensile specific strength 185 and 9/Cd,
The foam had a compression recovery rate of 85%, a heat shrinkage rate of 32%, and a good appearance.

Example 4 100 parts by weight of Shorex 6002B as a resin, 0.5 parts by weight of jetanolamine as a foaming moderator, 0.05 parts by weight of silica as a nucleating agent, and dichlorotetrafluoroethane and trichloromonofluoromethane as blowing agents. 25
A foam was obtained in the same manner as in Example 1 using parts by weight.

The obtained foam has a uniform and closed cell structure, the variation in the thickness of the cell membrane is within ±30%, the foam density is 0.0356 y/cd, the average cell diameter is 2.52 cells, and the cell size is 2.52 mm. Coefficient of variation in diameter 23%, specific tensile strength 155 K7/cn
It was an excellent foam with a compression recovery rate of 83% and a heat shrinkage rate of 22%.

Example 5 1.00 parts by weight of Zantek F180 as a resin, 1.5 parts by weight of jetanolamine as a foaming moderator, 1.5 parts by weight of Pronone 204, and 0.5 parts by weight of talc as a nucleating agent. A foam was obtained in the same manner as in Example 1, using 30 parts by weight of a mixture of dichlorotetrafluoroethane and methyl chloride in a molar ratio of 2:1 as a blowing agent. The obtained foam has an independent cell structure, the thickness variation of the cell membrane is within ±30%, and the foam density is 0.
,0240? /cni, average bubble diameter 0.09 mm,
Coefficient of variation of bubble diameter 56%, specific tensile strength 185 K9/c
ut, the compression recovery rate was 85%, the heat shrinkage rate was 35%, and although the appearance was slightly wrinkled, it was rated B and had commercial value.

Example 6 Zante Soku M 700 E 1.00 B as resin
Pronone 2082.0 as a foaming moderator for 7 parts
Part by weight, 0.0% magnesium stearate as a nucleating agent.
A foam was obtained in the same manner as in Example 1 using 40 parts by weight of a mixture of dichlorotetrafluoroethane and dichloromonofluoromethane in an equimolar ratio as a foaming agent. The obtained foam had a closed and uniform cell structure, a foam density of 0.0207 y/cA, and an average cell diameter of 0.
85M, the foam had excellent appearance and mechanical properties.

Comparative Example 8 A foam was obtained in the same manner as in Example 1 except that no nucleating agent was used. The obtained foam had independent cells, a foam density of 0.0217/cril, and an average cell diameter of 2.5%, but the variation in the thickness of the cell membrane exceeded ±30%, and the cell diameter The coefficient of variation was 77%, indicating that the foam lacked uniformity of cells and had poor mechanical properties.

Comparative Example 9 As a blowing agent, an equimolar mixture of dichlorotetrafluoroethane and trichlorotrifluoroethane was added to 100% of the resin.
A foam was prepared in the same manner as in Example 1 except that 8 parts by weight were added. The foam obtained had a foam density of 0.
], 18? /cnl, and the compression recovery rate is as low as 55%, which lacks flexibility.

Comparative Example 10 An equimolar mixture of dichlorotetrafluoroethane and trichlorotrifluoroethane was used as a developing agent for resin 10.
A foam was obtained in the same manner as in Example 1 except that 150 parts by weight was added compared to 0 parts by weight. The obtained foam had a foam density of 0.0065 f/ari and a high magnification, but the closed cell property was poor, the foam surface was severely wrinkled, the appearance was rated C, and the compression recovery rate was poor. It was low at 62%.

Comparative Example 11 Stearic acid (trade name: NAA), which has an effect of extending the foaming time of less than 1 second in the glass tube foaming test, and 0° NOF ■ were added to 100 parts by weight of the resin instead of the foaming moderator
1.0 parts by weight of
A foam was obtained in the same manner as in Example 1 except that parts by weight were used. The resulting foam has a foam density of 0.064'if
/cnl, and the appearance was evaluated as B, but the average cell diameter was coarse at 4.1 cells, and the compression recovery rate was low at 40%.

In addition, the birefringence test of the bubble film showed a non-uniform image,
Uniform expansion was not achieved during foaming /ζ0 Comparative Example 12 Example except that 40'li of dichlorotetrafluoroethane as a blowing agent and 6 parts by weight of talc as a nucleating agent were added to 100 parts by weight of the resin. A foam was obtained in the same manner as in 1. The properties of the obtained foam are that the foam density is 0.02
82? /cJ, but the average bubble diameter was 0.02m.
It was a foam with a fineness of m 2, poor closed-cell properties, uneven thickness and corrugation value of 100% or more, and no shape stability at all.

Comparative Example 13 100 parts by weight of Santic B870 as a resin, 15 parts by weight of jetanolamine as a foaming moderator,
Foaming was carried out in the same manner as in Example 1 using 0.05 parts by weight of Merck as a nucleating agent and 60 parts by weight of a mixed blowing agent in which dichlorotetrafluoroethane and trichlorotrifluoroethane were mixed at a molar ratio of 7:3 as a blowing agent. Get a body. The properties of the obtained foam are as follows: the foam density is 0.0158? /ct
However, the average bubble diameter was 2.3 mm, the coefficient of variation of the bubble diameter was 71%, and the bubbles lacked uniformity, and the closed cell property was poor and the compression recovery rate was low1. Table 1 Ll ) The amount of additive added is the weight per 100 parts by weight of the resin.
Y, 11;
1-5・l on the protrusion d-1, )-(, 11° saw fat mixed sound on the crow'G)
'T; Figure 2H shows )j fys tube o(, le s(
'・ Shows the state where the input manifold is heated and at 5-. , Figure 3 is a polarized light micrograph of the foam film of the present invention and the known foam.
IJ Form Ming Figure 1 Figure 2 Procedural Amendment (Method) August 24, 1988 1 Case Indication 1988 Patent Application No. 63300 2 Title of Invention Novel Foam and Process for Producing the Same 3 Amendments Relationship with the case involving the person who filed the patent application Patent applicant address: 1-2-6 Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture.
, (003) Asahi Kasei Shigyo Co., Ltd. Representative Miyazaki
4. Brief description of drawings and details of amendments to drawings (1) "As shown in Figure 3 a" in page 19 of the specification, line 8 of the same page As shown in Figure 1-3, delete ".

(2) As shown in the last line of page 37 to 1, figure 3b in the 1st line of page 38, and [3
First, delete the snow as shown in figure a.

(3) On page 38, lines 10 to 11, "as in Figures 3a and 3b" is corrected to "as in (a) and (b)."

(4) Delete "in Figure 3a" from line 9 on page 48.

(5) Delete "In Figure 3a" from the last line of page 49.

(6) Delete "Figure 3 is..." from lines 6 to 7 on page 64.

(7) Attached drawings Middle cylinder Figure 3 (al and Figure 3 (1) l
Delete.

Procedural amendment dated 8-0, 1982 1. Indication of the case 1988 Patent Application No. 63300 2. Name of the invention Novel foam and its manufacturing method 3. Person making the amendment 4. Relationship with U. Patent applicant Address: 1-2-6 Dojimahama, Kita-ku, Osaka-shi, Osaka Representative
Teru Miyazaki 4th Director 5 Date of amendment order Contents of spontaneous 8th amendment (1) The scope of the claims has been amended as shown in the attached sheet.

(2) In the 9th line of page 19 of the specification, ``Crosslinking'' adds the following sentence before J.

"It is necessary that the gel content is 10% or less, preferably 5% or less. This gel content is determined by mixing approximately 1 g of precisely weighed polyethylene with approximately 300 ml of dry xylene.
The sample was extracted by boiling for 0 hours, and the remaining insoluble portion was accurately weighed, and the weight was expressed as a percentage of the weight of the initial sample. ” (3) “Melting point 117” on page 20, line 8 of the same
°C or less "2" followed by ", preferably density 0.945 to 9
70 g/crd, melting point 122'C: or higher.

(4) Correct "2-natalpentene" in line 11 of page 20 to "2-methylpentene."

+511 JIE 20, page 1, line 15, "may be" is corrected to "may be, but it is necessary to include the ethylene component in an amount of 70 weight φ or more, preferably 80 fi or more relative to the total weight."I'm sorry.

(6) On the 21st page, line 6, next to ``Preferably 8'', it says ``More preferably, the melt index at a load of 21.6 Kp is 5 to 359 / 10 minutes, and the swell value is 30 to 509720 cm. "It is a thing." is used as a sword.

(7) "Stearyl di(aminoethylglycine)" in lines 4 and 5 of page 25 will be corrected to "stearyl di(aminoethyl)glycine."

(8) Add "preferably 0.002 to 3 parts by weight" next to "V 0.001 to 5 parts by weight" on the second line of page 26.

(9) Change “rso section” from the bottom 3 lines from the bottom of page 27 to “10”
I will correct it to 0 person in charge.

00) Change "40 Section" from the bottom three lines of page 35 to "
I will correct it to ``50 Section.''

(11) On page 36, lines 10 and 11, "If the film thickness is thin, VC is (1μ or less)" will be corrected to "If the film thickness is thin, for example 20μ or less,".

(12) rX+-also/e× on page 37, line 2
100 (chi)" to r (XI-X)/xtoo (%)"
I will correct it.

(13) On page 37, line 3, [Anti-X2/Also ×
Correct 100 (person in charge) to "(X-X2)/XX100 (person in charge)".

(14) rf71J on page 38, line 13
[Corrected to 81J.

(15) 9 lines from the bottom of page 39, r-ts+”
will be corrected in September.

(16) In the first line of page 41, “(September is “(1
Corrected to ``.

(17) Correct "(1 no)" in the bottom two lines of page 41 to r (11) J and edit.

(18) r in the 3rd line from the bottom of page 42 (11)
Correct J to r (12) J.

(One) 9th line from the bottom of page 43 rt::l
Next to "Corrugate value of foam", add the following text on a new line.

``This is a factor for evaluating relatively large wrinkles, threads i''L, etc. of the foam, and is measured as follows. ” (difficult)
From the bottom of page 43, lines 4 to 3, "Place this foam on a flat surface." Press the surface of the foam with an average force until it reaches 100 degrees, then shake it off.

■) On page 44, line 10 from the bottom, after rtli) "Surface smoothness of foam", add a new line and add "J, which is a factor that evaluates the presence or absence of small irregularities on the surface of foam.

(22) In the 3rd to 2nd line from the bottom of page 44, "Place it on a flat surface without applying force" to "Place it on a flat surface, so that the uneven convexities on the surface of the foam are as much as possible without being crushed." , press down evenly on the foam surface so that it touches a flat surface.''

(23) Correct the "length and width" in the 5th line from the bottom of page 44 to "original length and width" and edit.

(24) On the last line of page 44, the next f
Add ``Repeat this for the front and back sides,'' and finish.

(25) Delete "Observe from the longitudinal side of the foam cross section" in line 6 of page 45.

(26) “Numbers 1 to 6” in line 7 of page 49 will be corrected to “Numbers 1 to 9.”

(27) From the bottom of page 50, change “inferior” in line 6 to “
The variation in the thickness of the inferior bubble film exceeds ±30 factors.''

(28) Correct "jetanolamine" in line 12 of page 51 to "di-2-hydroxyethylamine" and omit it.

(29) On page 52, line 6, "jetanolamine" is corrected to "di-2-hydroxyethylamine."

(30) “Comparative Example 8” on page 53, line 9 of the same page is changed to “
``Comparative Example 9'', 4 lines from the bottom of the same page, ``Comparative Example 9j'' [
Comparative Example 10J has been corrected.

(31) "Comparative Example 10J" in the 5th line of page 54 is changed to "Comparative Example 11", and "Comparative Example 11" in the 14th line of the same page
I will correct it to "Comparative Example 12".

(32) Change “Comparative Example 12” in the 7th line of page 55 to “Comparative Example 13” and change “Comparative Example 13” in the 5th line from the bottom of the same page to “Comparative Example 13”.
” to “Comparative Example 14”.

(33) On page 55, 3 lines from the bottom, the text has been corrected to read "Jetanolamine Jkr di-2-hydroxyethylamine."

(34) Same No. 57 Base) Additive 0 agent in the experiment number 9 column of Table 1 [Poly G200PJ
K Correct and edit.

(35) Foaming time r2 in the experiment number 32 column of Table 1 on page 57. Correct sJ to r2.6J.

(36) In Table 2 of Section 58 Hage, ``(including di-2-hydroxyethylamine)'' will be added next to ``amide'' in the name (main component) in the column for Stapome F.

(379, page 58, Table 3, the product name display "Poly G-200PJ" has been changed to "Poly G 2020PJ [Corrected.

(38) l'- in the item column of Table 5 on page 61
Correct the HM month to "Melt Index".

(39) In Table 7 on page 63, the addition amount of Anon BF in the column of actual flow example 2, experiment number 9 will be corrected to ``1''.

(In Table 7 on page 63 of 4, the coefficient of variation of bubble diameter in the column of Comparative Example 8, Experiment No. 13 is corrected from ``69'' to ``79.''

Claims] 100 parts by weight of substantially non-crosslinked polyenalene with a density of o, q3sy/cJ or higher and a melting point of 117°C or higher, which has a foaming time of Foaming moderator 0.0 with full ability to extend for more than 1 second
Obtained by foaming a composition containing 5 to 10 parts by weight,
Consisting of closed cells with an average cell diameter of 0.05 to 3 mm, the foam density is 0007 to 0.10 g/cd, the variation in the thickness of the cell membrane is within ±30 coefficients, and the coefficient of variation of the cell diameter is 70 coefficients or more. Foam material with "Totokin" S character.

2. The foam according to claim 1, which exhibits physical properties such as tensile specific strength of 150 K9/cr4 or more, compression recovery rate of 80φ or more, 7 Jl] and heat shrinkage rate of 50 coefficients or less.

3. The foam according to claim 1, which has a thickness unevenness of less than 50 mm, a corrugation value of less than 100 mm, and a surface smoothness of less than 2 mm.

4 Polyx Ten at 190°C, 21,6 to 9, melt index 0.02-40g710 minutes, swell value 20-50,! The foam according to claim 1, which has a diameter of 9720 cm or more.

5 The foaming moderator has the general formula % (in the formula, Ri is an alkylene group having 1 to 5 carbon atoms, A is a hydrogen atom or an acyl group, n is an integer from 1 to 1o, and X is 0 or 1 to
is an integer of 2] The foam according to claim 1, 2, 3, or 4, which is a compound represented by the following.

6 The foaming moderator has the general formula % (in the formula, R2 is a divalent hydrocarbon group having 1 to 6 carbon atoms, and each R
2 may be the same or different and is an integer of ml-i1 or more) The foam according to claim 1, 2, 3, or 4, which is a compound represented by the following formula.

7 The foaming moderator has the general formula HO2R, O9BAR40〒R30KanH (R3 and R4 in the formula are logically different divalent hydrocarbon groups having 1 to 6 carbon atoms, and a, b and 8. The foam according to claim 7, wherein C is an integer from 1 to 2.

9 For 10N of substantially non-crosslinked polyethylene with a density of 0.935&/cJ or higher and a melting point of 117°C or higher, the Tohibe foaming time is 1 second or more in the case of a glass tube foaming test method A with no additives. Foaming moderator O, O with ability to extend
The composition obtained by foaming a composition containing ~10 parts by weight of S~10 parts by weight and 0.001~5 parts by weight of a nucleating agent can be obtained by foaming a composition containing ~10 parts by weight of S ~10 parts by weight.
It is composed of 3-closed cells, and the foam density is 007 to 0.
-10g/cTI, bubble membrane thickness variation ±30%
An expanded foam characterized by a coefficient of variation of cell diameter within 70%.

10. The foam according to claim 9, which exhibits physical properties such as a tensile specific strength of 150 K9/cr1 or more, a compression recovery rate of 80 factors or more, and a heat shrinkage rate of 50% or less.

U The foam according to claim 9, which has a thickness unevenness of less than 50%, a corrugation value of less than 5°, and a surface smoothness of less than 2 groups.

12 Polyethylene at 190℃, 21, 6 to 7K
Nord index 0.02-40I/10 minutes,
The foam according to claim 9, which has a swell value of 20 to 50 and a radius of 720 cm or more.

13 The foaming moderator has the general formula % (in the formula, R is an alkylene group having 1 to 5 carbon atoms, A is a hydrogen atom or an acyl group, nl'j: an integer of 1 to 10, and X is 0 or 1 to Claims 9 and 10 are compounds represented by
The foam according to item 1, item 11 or $12.

14 The foaming moderator has the general formula % (in the formula, R2 is a divalent hydrocarbon group having 1 to 6 carbon atoms, and each R2
may be the same or different, and m is an integer of 1 or more.
The foam according to item 0, item 1J or item 12.

15 The foaming moderator is of the general formula) IO (-R30, R40, R30,
and R4 are different divalent hydrocarbon groups having 1 to 6 carbon atoms, and a, b and C are integers of 1 or more.
16. The foam according to claim 15, which is composed of the following formula: R3 car CB2 C'2- group and R4 car 0H-CH2- group.

17 (a) Density o9359/cA or higher, melting point 11.7
For 100 parts by weight of substantially non-crosslinked polyethylene of C or higher, (b) A foaming moderator that has the ability to extend the foaming time by 1 second or more compared to the case without additives in the glass tube foaming test 1 test method. 0.05 to 10 parts by weight and H nucleating agent o, ooi~
A composition containing 5 parts by weight of a composition is heated and kneaded together with a volatile organic blowing agent at a temperature above the melting point of polyethylene under high pressure, and is continuously foamed while being extruded from a high temperature and high pressure region to a low temperature and low pressure region. Consists of closed cells with a diameter of 0.05 to 3 mm, and a foam density of 0.007 to O-1.0
17c! d, variation in the thickness of the bubble film is within ±30%,
A method for producing a foam having a cell diameter coefficient of variation of 70 or less.

18. The manufacturing method according to claim 17, wherein the volatile organic blowing agent is used in an amount of 10 to 140 parts by weight based on 100 parts by weight of polyethylene.

19 Poly: f-chain melt index at 190°C, 21,6 to 9VC 0.02 to 40. ! 7
/10 minutes, swell value 20-50 l/20 cm
The manufacturing method according to claim 17, which is the above.

20 The foaming moderator has the general formula (H) An integer from 1 to 10, X is 0 or 1 to
The manufacturing method according to claim 17 or 18, which is a compound represented by:

21 The foaming moderator has the general formula % formula %] (R2 in the formula is a divalent hydrocarbon group having 1 to 6 carbon atoms, and each R2
may be the same or different, and m is an integer of 1 or more.

22 The foaming moderator is represented by the general formula % (in the formula, R5 and R4 are different divalent hydrocarbon groups having 1 to 6 carbon atoms, and a, b and C are integers of 1 or more). The manufacturing method according to claim 21,
9Ht23 In the general formula (7) RJ''-CH2CH2- group, R, Ka, -cH, -
23. The manufacturing method according to claim 22, which is 0H2-.

24. The manufacturing method according to claim 17 or 18, wherein the volatile organic blowing agent comprises at least one hydrocarbon.

25. The production method according to claim 24, wherein the halogenated hydrocarbon is a mixture of dichlorotetrafluoroethane and other halogenated hydrocarbons.

26. The manufacturing method according to claim 25, wherein the molar ratio of dichlorotetrafluoroethane and other halogenated hydrocarbons is 1:4 to 4:1.

27 A patent in which the halogenated hydrocarbon other than dichlorotetrafluoroethane is at least one selected from trichloromonofluoromethane, dichloromonofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, methyl chloride, and dichloridemethane The manufacturing method according to claim 25 or 26.

Claims (1)

[Claims] 1. Density 0.935 g/at1 or more, melting point 117
For 100 parts by weight of substantially non-crosslinked polyethylene at a temperature of 0.05 to 0.05 °C, a foaming moderator with a foaming capacity of 0.05 to 100% that extends the foaming time by 1 second or more compared to the case without additives in the glass tube foaming test method. The composition obtained by foaming a composition containing 10 parts by weight is composed of closed cells with an average cell diameter of 0.05 to 3 m, a foam density of 0.07 to 0.1 oy/ad, and a variation in the thickness of the cell membrane of ± A foam having a coefficient of variation of 30 or less and a coefficient of variation of bubble diameter of 70 or less. 2. The foam according to claim 1, which exhibits physical properties such as a tensile specific strength of 150 K7/CR4 or more, a compression recovery rate of 80 factors or more, and a sword mouth heat shrinkage rate of 50 factors or less. 6. The foam according to claim 1, which has a thickness unevenness of less than 50 coefficients, a corrugation value of less than 50 coefficients, and a surface smoothness of less than 2 mm. 4. The foam according to claim 1, wherein the polyethylene has a melt index of 0.02 to 40 g/10 min at 190° C. and 21.6 to 9, and a swell value of 20 to 50 g/720 cm or more. 5 The foaming moderator has the general formula % (in the formula, R is an alkylene group having 1 to 5 carbon atoms, A is a hydrogen atom or an acyl group, n is an integer of 1 to 10, and X is 0 or 1 to
2) is an integer of 2). Claims 1 and 2
3. The foam according to item 3, item 4, or item 4. 6 The foaming moderator is expressed by the general formula % (in the formula, R2 is a divalent hydrocarbon group having 1 to 6 carbon atoms, and each R2
may be the same or different, and m is an integer of 1 or more. 7 The foaming moderator has the general formula HO (g-R〇〆〆R40shows R30tanJ (R3 in the formula
and R4 are divalent hydrocarbon groups each having 1 to 6 carbon atoms, and a, b and C are integers of 1 or more. 9 density 0.935. r/crdr, melting point 117°C
For 100 parts by weight of the above-mentioned substantially non-crosslinked polyethylene, the foaming time was extended by 1% or more compared to the case without the additive in the glass tube foaming test method, and no foaming moderator with foaming ability was added.
．． 05-10] obtained by foaming a composition containing i part by weight and 0.001 to 5 parts by weight of a nucleating agent, average cell diameter 0.05
The foam is characterized by consisting of ~3~3 closed cells, the variation in the thickness of the foam membrane is within ±30 coefficients, and the coefficient of variation of the cell diameter is within 70 coefficients. 10. The foam according to claim 9, which exhibits physical properties such as a tensile strength of 15oK9/cribr, a compression recovery rate of 80 or more, and a heat shrinkage of 450% or less. 11. The foam according to claim 9, which has a thickness unevenness of less than 50%, a corrugation value of less than so%, and a surface smoothness of 2 degrees. 12 The foam according to claim 9, wherein the polyethylene has a melt index of 0.02 to 40.9710 minutes at 190°C, a melt index of 21.6 to 7, and a swell value of 20 to 50 g/20 cnr or more. . 16 Foaming moderator has the general formula % formula %) (In the formula, R is an alkylene group having 1 to 5 carbon atoms, A is a hydrogen atom or an acyl group, n is an integer from 1 to 1o, and X is O or 1 to
Claims 9 and 10 are compounds represented by
The foam according to item 1, item 11 or item 12.1J-1. 14 The foaming moderator has the general formula % formula % (R2 in the formula is a divalent hydrocarbon group having 1 to 6 carbon atoms, and the valley R2
may be the same or different, and m is an integer on the tool] Claims 9 and 10 are compounds represented by
The foam according to item 1, item 11 or item 12. 15 The foaming moderator is expressed by the general formula % (in the formula, R5 and R4 are different divalent hydrocarbon groups having 1 to 6 carbon atoms, and a, b and C are integers of 1 or more. The foam according to claim 14. In the general formula H3 16, 0) R= is -0H2C! 16. The foam according to claim 15, wherein the H2- group has the formula -CH-CH2-. 17 (a) Density mouth 935,! 7/ c! Substantially non-crosslinked polyethylene 100 with a melting point of 117° C. or higher and a melting point of 117° C. or higher
(b) In the glass tube foaming test method, compared to the case without additives, the foaming time is extended by 1 second or more compared to the case without additives. oo
A composition containing i to 5 parts by weight is heated and kneaded together with a volatile organic blowing agent at a temperature above the melting point of polyethylene under high pressure, and is continuously foamed while being extruded from a high temperature and high pressure region to a low temperature and low pressure region. Consists of closed cells with an average cell diameter of 0.05 to 3 degrees, and the thickness θ variation of the foam membrane is ±go.
% or less, and a cell diameter variation coefficient of 7096 or less. 18. The manufacturing method according to claim 17, wherein the volatile organic blowing agent is used in a proportion of 10 to 140 parts by weight per 100 parts by weight of polyethylene. 18. The manufacturing method according to claim 17, wherein the polyethylene has a tart index of 0602 to 4097.10 minutes and a swell value of 20 to 50 g/20 am or more at 190°C and 21.6 g/20 am. 20 The foaming moderator has the general formula % formula % (0 in the formula) R is an alkylene group having 1 to 5 carbon atoms, A is a hydrogen atom or an acyl group, n &'11 to 100) q number, X is O or 1 ~20) is an integer) is a compound represented by the special plan expression QQ σ, . 21 foaming moderator has the general formula HO(-R209H (in the formula, R2 is a divalent hydrocarbon group having 1 to 6 carbon atoms, and each R2
may be the same or different, and m is an integer of 1 or more. η The foaming moderator has the general formula % (in the formula, R6 and R4 are different divalent hydrocarbon groups having 1 to 6 carbon atoms, and a, b and C are integers of 1 or more). 25. In the general formula, R3 is -CH20H2- group, R4 is -H-C
23. The manufacturing method according to claim 22, wherein H,,-. 24 Volatile organic blowing agent is halogenated carbonized-lk
．． The manufacturing method according to claim 17 or 18, comprising at least one building. 25. The manufacturing method according to claim 24, wherein the halogenated hydrocarbon (B) is a mixture of dichlorotetrafluoroethane and other halogenated hydrocarbons. The mixing ratio of 26 dichlorotetrafluoroethane and other halogenated hydrocarbons is 1:4 to 4:
26. The manufacturing method according to claim 25, which is No. 1. 27 A patent in which the halogenated hydrocarbon other than dichlorotetrafluoroethane is at least one selected from trichloromonofluoromethane, dichloromonofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, methyl chloride, and dichloridemethane The manufacturing method according to claim 25 or 26.