JPS59172531A - Production of resin foam by using aqueous medium - Google Patents

Abstract

PURPOSE:To obtain a high-quality resin foam at a high production rate, by allowing an aqueous medium to adhere to porous aggregates comprising partially fused thermoplastic resin powders or particles coated with a hydrophilic fine solid powder, melt-mixing the mixture under pressure, and expanding the molten mixture. CONSTITUTION:Powders or particles of a thermoplastic resin such as polyethylene or polypropylene are mixed with a hydrophilic fine solid powder which does not melt at the melting temperature of the resin (e.g., talc or silica) by means of a mixer or the like, whereupon the surfaces of the resin powders or particles are coated with the hydrophilic fine solid powder and at the same time a number of the powders or particles are brought together to form porous aggregates. A resin compound comprising these porous aggregates is treated with an aqueous medium (e.g., water) to allow said medium to adhere to the porous aggregates. This compound is melt-mixed under an elevated pressure under which evaporation of the aqueous medium is controlled, and expanded by releasing it from the pressurized state to obtain the purpose resin foam.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for foaming thermoplastic resins, and more specifically, to foaming thermoplastic resins using an aqueous medium as a foaming agent.
1 relates to a method of manufacturing a foam.

Conventionally, methods for producing thermoplastic resin foams include co-trapping thermoplastic resins with thermally decomposable blowing agents that decompose by heating to generate primary hydrogen gas and carbon dioxide, and low-boiling liquids or liquefied gases. The method used is to melt and knead under pressure and then lower the pressure to foam. However, in the case of thermally decomposable foaming agents, decomposition residues are generated which cause coloring and bad odor of the resin foam, and it is also difficult to control foaming. On the other hand, when a low boiling point liquid or liquefied gas is used as a blowing agent, there are risks such as flammability, explosiveness, and hygiene of the blowing agent during storage of expandable beads and foams or during the foaming process. There is a problem in handling.

The present inventors have conducted extensive research into a method for producing thermoplastic resin foams that does not have the above-mentioned drawbacks, and have found that if an aqueous medium is used in combination with a hydrophilic solid fine powder, thermoplastic resins can be easily produced in an aqueous medium. They discovered that it can be foamed and completed the present invention.

Therefore, according to the present invention, (α) the thermoplastic resin powder and the resin powder partially embedded in the surface of the resin powder have a substantially A resin compound consisting of a partially fused porous agglomerate of thermoplastic resin powder coated with a hydrophilic solid fine powder that does not melt in the water is treated with an aqueous medium to (b) melt-kneading the resin compound treated with the aqueous medium under pressurized conditions that substantially suppresses evaporation of the aqueous medium; (C) There is provided a method for producing a resin foam using an aqueous medium, which is characterized in that the melt-kneaded resin composition is then released from the pressurized condition and foamed.

Water is a liquid with a relatively low boiling point, so in theory it can act as a foaming agent for the thermoplastic phase, but it is generally not compatible with hydrophobic resins, so fillers added to resins are dry. It can be used after removing moisture. Therefore, in the past, it was completely unthinkable to use water as a foaming agent for resins. However, the fact that this has been made possible by the method of the present invention is something that could not have been expected from the prior art, and is therefore revolutionary.

According to the method of the present invention, since an aqueous medium that consumes a large amount of latent heat of vaporization is used as a foaming agent, unlike air foaming of an aqueous medium, melt extrusion at a relatively high temperature and high speed is possible.
High quality resin foam can be manufactured with high productivity. Furthermore, the method of the present invention does not produce decomposition residues that color the resin or generate bad odors, unlike thermally decomposable blowing agents, and the aqueous medium used in the present invention is It is a blowing agent that is clean and easy to handle in terms of explosiveness, hygiene, etc. when injected into liquids or liquefied gases with a low -118 point.

Therefore, the method of the present invention is industrially extremely advantageous as a method for producing thermoplastic resin foams.

Hereinafter, the method of the present invention will be explained in detail.

The thermoplastic resin used in the method of the present invention is not particularly limited, and any resin conventionally used for plastic molding of each building can be used, such as high-density polyethylene, low-density polyethylene, polypropylene,
Olefin resins such as polybutene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, petroleum resin; Tzene resins such as polybutadiene and polyisogrene; polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, polyvinyl alcohol, etc. vinyl resin.

Acrylic resins such as polymethyl methacrylate; Styrenic resins such as polymethylene, acrylic-styrene copolymer, and acrylic-butadiene-styrene copolymer; Polyamide resins such as nylon-6, -66, and -12;
Included are polyester resins such as polyethylene terephthalate. Each of these can be used alone, or two or more kinds can be used in a blend.

On the other hand, the above 91! I! The hydrophilic solid fine powder used in conjunction with the hydrophilic solid powder is either hydrophilic itself or is made of an organic or inorganic substance that has been rendered hydrophilic by a hydrophilic treatment.

Further, the hydrophilic solid fine powder used in the present invention does not substantially dissolve at the melting temperature of the resin powder used together with the hydrophilic solid fine powder, and desirably may swell with an aqueous medium. , selected from those that do not dissolve easily. That is, those having a solubility in water at 25° C. of generally 1 ol/l or less, preferably 5〃/l or less are advantageously used.

Examples of hydrophilic solid fine powders that can be suitably used in the present invention include: shell powders such as starch and wheat flour; plant powders such as wood flour; urea resins, melamine resins, phenolic resins, etc. Examples include hydrophilic resin powders such as iron, aluminum and other gold powders, talc, clay, calcium carbonate, silica, alumina, glass powders and other inorganic powders. These solid fine powders have sufficient hydrophilicity by themselves, but sometimes they can be treated with substances (hereinafter referred to as surfactants) that make the surface of these fine powders more susceptible to water (hereinafter referred to as surfactants), such as , fatty acid alkanolamide, fatty acid monoglyceroid, polyethylene glycol fatty acid ester, and other nonionic surfactants; fatty acid amide,
Anionic surfactants such as fatty acid metal salts, alkyl sulfate types, and alkyl phosphate types; Cationic surfactants such as A〉Lium salts; Fatty acids; Polyhydric alcohols such as polyethylene glycol, polypropylene glycol, and glycerin; Polyethylene glycol soethyl By surface treating with ethers such as ether, polyvinyl alcohol, etc., or a mixture thereof, it is possible to further increase hydrophilicity and improve affinity bonding between the resin and the fine powder.

In addition, even if the substance is hydrophobic, it can be made hydrophilic by treating the surface with a surface active substance such as the one mentioned above, or a hydrophilic substance such as polyvinyl alcohol, fatty acids, polyhydric alcohols, or ethers. Then, it can be used in the same way as the parent aqueous substance mentioned above.

The hydrophilic solid fine powders described above may be used alone or in combination.
Combinations of one or more species can be used.

In the present invention, talc, calcium carbonate, clay, silica, and alumina having an average particle size of 1 to 15 microns are particularly preferably used.

In addition, a part of the Queen's hydrophilic solid fine powder, generally up to 20% by weight, preferably 10% by weight or less of the total amount of the solid fine powder used, may be added to, for example, cotton, silk, linen, wool, synthetic Fibers, organic short fibers such as recycled fibers, or moth and lane fibers (
Inorganic short fibers such as carbon fiber and asbestos may be substituted, and by using these short fibers in combination, the mechanical strength of the foam can be significantly improved.

The particle size of the hydrophilic solid fine powder used in the present invention is not strictly limited, and may be varied widely depending on the desired degree of foaming, the properties of the resin, the physical properties required of the foam, etc. However, it is generally appropriate that the average particle diameter is 100 microns or less, preferably in the range of 0.1 to 50 microns, and more preferably in the range of 0.5 to 30 microns. In addition, when using short fibers as mentioned above,
The fiber length is generally 1Off or less, preferably 5#IIl or less, and the fiber diameter is generally 100 microns or less.

Preferably, it is in the range of 1 to 50 microns.

As mentioned above, from the thermoplastic resin and the hydrophilic solid fine powder, the thermoplastic resin coated with the hydrophilic solid fine powder is attached and buried in an exposed (exposed) state on the surface of the resin powder. (However, of course, the resin powder may further contain the solid fine powder dispersed therein). The amount of solid fine powder embedded in the resin powder is such that the surface of each resin powder is mostly covered with f + the exposed solid fine powder,
It is desirable that the amount be such that the base of the resin powder particles can hardly be seen when observed with an electron microscope at a magnification of 300 times.

Moreover, a large number of resin powder particles coated with hydrophilic solid fine powder exposed in this manner aggregate, and the individual powder particles partially adhere to each other to form a porous mass. is important. When such a porous aggregate is treated with an aqueous medium, it must be capable of stably adhering and retaining the aqueous medium, and therefore, the porous aggregate must have a water vapor adsorption rate of at least 0,
0.5%, preferably 0.3% or more.

By the way, "water vapor adsorption rate" refers to the porous aggregate of WsQ that has been kept in a constant temperature and humidity room at a temperature of 25°C, a relative humidity of 30%, and a pressure lαtm for 24 hours, at a temperature of 105°C and a water vapor pressure of 1. .If the ribs were kept in a closed atmosphere of 2 atm for 1 hour, taken out and left on paper for 3 minutes, then placed in a drying oven at 105°C for 3 minutes, and immediately weighed and the amount was taken as WtQ, the following A value calculated by a formula.

The thickness of the above-mentioned porous aggregate is not important and can be any size, but from the viewpoint of ease of handling and melt-kneading described below, it is generally 0, 1 to 20 rm, preferably 0 to 3 rm. Particles with a particle size range of 5 mm are suitable. Therefore, if the particle size is larger than this, the pulverizer 1. It is preferable to use the powder after making it into a particle size within the above-mentioned range using a grinding machine or the like.

One promising method for preparing such porous aggregates is to mix the aforementioned thermoplastic resin and hydrophilic solid powder in a high-speed (vortex) mixer at a temperature above the melting temperature of the Lely plastic resin. This is a high-speed mixing method. This high-speed mixing generally takes about 50 to about 250 seconds, preferably about 70 to about 20 seconds, from the point at which the motor's rotational resistance fluctuates and increases.
This continues for 0 seconds 1IA5, after which the melted and mixed resin composition is discharged from the midge. A porous aggregate is obtained by this process.

The ratio of the hydrophilic solid fine powder to the thermoplastic resin when charging into the above-mentioned mixing mixer is determined by the type of resin and solid fine powder, the water absorption rate required for the resulting porous aggregate, and the water vapor content. This may vary widely depending on the adsorption rate, etc., but in general, the amount of solid fine powder is 30 to 250 parts by weight, preferably 60 to 15 parts by weight, per 100 parts by weight of the thermoplastic resin.
They can be used alone or in combination at a ratio of 0 parts by mass, preferably 80 to 120 parts by mass. It is appropriate that the amount is less than % by weight, preferably less than % by weight of io vehicle.

In addition, when preparing the above-mentioned porous aggregate, in addition to the resin and solid fine powder, resin additives such as antioxidants, surface active 411, colorants, ultraviolet absorbers, flame retardants, etc. may be added as necessary. good. Examples of antioxidants that can be used include thioglobionic acid ester antioxidants such as solauryl thiosprobionate; phenolic antioxidants such as alkylphenols and alkylbisphenols;
; or a mixture thereof, and examples of the surfactant include those mentioned above. The antioxidant can generally be dosed in a proportion of 0.1 to 10 parts by weight per 100 tons. In addition, examples of coloring agents include dyes and pigments such as tania, phthalocyanine blue, and azo dyes, and examples of ultraviolet absorbers include ultraviolet absorbers such as evasalicyl, benzophenone, and benzotriazole. As flame retardants, phosphoric acid esters, halodanized hydrocarbons, antimony oxides, and other flame retardants that have been conventionally used as additives for wood can be blended in normal amounts.

The porous agglomerate thus MN''lA is used as is as a resin compound and treated with an aqueous medium as a blowing agent according to the method of the invention.

Generally, aqueous media can be used, but adjusting the boiling point and vapor pressure of the medium, increasing the affinity for the porous aggregate,
For the purpose of improving the dispersion stability of the aqueous medium during melt-kneading of resin compounds and improving the uniformity of bubbles, it is convenient to add surfactants, water-soluble polymers, polyhydric alcohols, water-miscible organic solvents, etc. to water. Can be added. The above-mentioned surfactants can be used, and these can be added to water at a concentration of generally 1 to 50 y/l, preferably t-tog/l. In addition, as water bathable polymers and polyhydric alcohols, for example, the degree of polymerization is about 50.
0 to about 2000 and a degree of saponification of 85% or more, mono- or polyethylene glycols having a number average molecular weight of up to 400, glycerin, etc., which are generally 1-10011/l relative to water, preferably It can be added at a concentration of 10 to 501/l.

Furthermore, examples of the water-miscible organic solvent used include Eva,
Alcohols such as methanol, ethanol, furonol, cyclohexanol, etc.; esters such as 6% ethyl, butyl acetate; diethyl ether, soxane,
Ethers such as trioxane; ketones other than acetone and methyl ethyl ketone;
100.9/A', preferably 10 to 50 g/II. As mentioned above, the use of the hobbed aqueous barrier can vary widely depending on the expansion ratio desired for the foam, etc. Although it can vary over a wide range, it is generally the same as above, 100 parts per part. ~1515 parts by weight Preferably 2 to 5 parts by weight The treatment of the paddle/T fat compound with a monoaqueous body is carried out by combining the two and blending them in a mixer. It will come out.

The melt-kneaded state oil powder treated with the aqueous medium is then kneaded under pressurized conditions that substantially suppresses the expansion of the aqueous medium. It can be carried out in the same way as the #day mixed line during the regular delivery of resin foam, and it can be carried out using an extruder such as a non-vent single screw extruder or a non-vent multi-screw extruder. . Here, [pressurized conditions under which evaporation of the aqueous medium is substantially suppressed;
] means that the output conditions are determined by the vapor pressure of the aqueous medium soaked in the resin compound at the melt kneading temperature. There are six things you can do.

The resin composition sufficiently kneaded in this way has a fa
The material is extruded in a molten state through die lips of various shapes, placed in a suitable mold, or applied to a press molding machine, released from the pressurized state 17, and foamed and solidified. As a result, resin foams processed into shapes such as corrugated sheets, flattened sheets, stretched sheets, irregularly shaped extrudates, etc. can be obtained. Construction 11. : It has various disadvantageous advantages as described below.

(a) Conventional polyethylene, polypropylene, etc.
1 (1) First/It was considered technically difficult to industrially perform striped foaming on fin-based resins, but according to the present invention, even non-crosslinked polyolefin-based 4\1.1 resins can be easily foamed with +y+5. It is possible to make a foam with a closed cell structure that is uniform and narrow in magnification.

(b) Conventionally, it was virtually impossible to produce resin foam containing a large amount of filler, but according to the method of the present invention, resin foam containing a large amount of filler can be produced industrially. can be easily manufactured.

(C) According to the method of the present invention, A can be achieved by melting and extruding the resin at a higher temperature and higher speed than in the past, so that high quality resin foam can be produced with good productivity.

(Ii) According to the method of the present invention, since an aqueous medium with a large evaporation concentration Q is used as a foaming agent, as mentioned above, the foaming film strength is significantly reduced, resulting in the formation of fine and uniform closed cells. can do.

(e) Unlike conventional thermally decomposed foaming agents, no decomposition residue is produced, and the resin does not become colored or generate bad odors. Additionally, unlike conventional low-boiling liquids and liquefied gases, it is not flammable, explosive, or sanitary.

(7') The foaming operation is not complicated and the equipment used is simple, making it possible to produce resin foam at low cost.

(g) It is easy to control foaming, and it is possible to freely create foams with small foaming ratios (volume ratios from about 2 times to about 30 times). According to the method of the invention, a resin foam having a skin layer can be easily produced.

The method of the present invention will now be further illustrated by examples.

Example 1 9. 9 Resin: Polypropylene (Noblen MA-sA manufactured by Mitsubishi Yuka Co., Ltd.; Mi = 0.7, density = 0.9> 10.00
0 Fine powder: Talc (Japan Talc Inc. MS; average particle size 9/J) 10,000 Surfactant: Fatty acid alkanolamide (Amizole LDE manufactured by Kawaken Fine Chemicals Co., Ltd.) 100° Fatty Acid Monoglycerite (Riken Vitamin Co., Ltd.) Riquemar S-100150 Fatty acid amide (Alflo P-10, manufactured by NOF Corporation) 50 Coloring agent: r!R-modified titanium natase 11 A100, manufactured by Shikiishihara Sangyo Co., Ltd.) 500 Antioxidant: Dilauryl thiodipropinate 301.
1.3-Tris(2-methyl-4-hydroxy-5-8MG l 00 mixed electric motor 22KW 4P/8PI
The mixing tank (tank capacity: 100J) was heated by circulating heating oil at 140° to 150°C through the jacket.The entire mixture was put into the mixing tank of the mixer and mixed at high speed.

After about 20 minutes, the mixing IC current began to fluctuate and increase (mixture temperature: 195°C), and stopped after 80 seconds.
8OA in 0 seconds (total 120 seconds) (mixture temperature 210°C)
I opened the outlet and released the mixture.

The ejected mixed proboscis is rapidly cooled and coarsely crushed by a low-speed rotating mixer with strong air cooling, to form a resin composite consisting of a partially fused porous aggregate of resin powder coated with powder. Obtained.

Then, it was crushed to a maximum particle size of 5 degrees or less using a crusher (Morita 4 Seisakusho TC-3 type 3) P), and the mixture was crushed at 50 to 300 r, p,
m, transfer to a mixer with mixing rotation, and add 1 alkylbenzene sulfonate (Nissan Nurex H manufactured by Nippon Oil & Fats Co., Ltd.)
Add an aqueous medium containing s, o o o cc of tap water (2,5 parts by weight based on 100 tonne of resin concrete land) and mix for 5 minutes or more to prepare a resin concrete that has been impregnated with an aqueous medium. It was set to z4 round.

A circular die is attached to the 70-order extruder, and air rings are installed inside and outside the die rig to cool the tip of the die ring and the produced sheet.The circular die/mandrel blow ratio'k is set to 1.8 times, and the mandrel is cooled with hot water. The outer periphery is cooled by an air ring, and the extruder cylinder has a maximum temperature of 225°C and a die quality of 195°C.
(A film was formed by foaming and extrusion using the four-miya fat temperature bond.

Most of the foam was homogeneous with a diameter of 0.5 tmμ and 0.1 to 0.3 fi, and the foaming ratio (body + j #, magnification) was 9.8 times.

This foam sheet is suitable for use in food packaging containers such as T1/- by true molding and pressure forming, and is also suitable for use as a cushioning material and white paperboard. used for.

Example blending amount gI Resin: low density, l IJ ethylene (Tubatic L manufactured by Mitsubishi Kasei Co., Ltd. FIOIA; MI = 0.45, density = 0.9221 10,000 fine powder double quality calcium carbonate (Whiten manufactured by Shiroishi Calcium Co., Ltd.) SSB; average particle size 1.5 μl &000 ton calcium carbonate (Whiten B, Shiraishi Calcium Co., Ltd.; average particle size &6 μl) 7.000 Surfactant: Fatty acid alkanolamide (Amizol cDE l' 120, manufactured by Kawaken Fine Chemical Co., Ltd.) ;
1? Liethylene glycol (PEG6000 manufactured by Seishikasei Co., Ltd.) 60 Colorant Neated titanium (anatase type, manufactured by 6 Hara Sangyo Co., Ltd. A 100) '300 Cobalt aluminate blue (published by Dainichi Fusei Kasha!) O, l
Antioxidant: Cyclic neopentanetetolyl bis i.

22'-Methylenebis(4-methyl-6-t-butylphenol) 20 Nonylphenyl phosphite 10 Using the same high-speed mixer as in Run 111, charge the entire formulation and
After about 16 minutes of rapid mixing, the mixture temperature was 190°C), and after 120 seconds, one fish rose and reached 5OA (mixture temperature 200°C) in 10 seconds (total of 125-130 seconds), so it was discharged. The outlet was opened and the mixed proboscis was released.

The discharged mixture is rapidly cooled and coarsely crushed by a low-speed rotating mixer with strong air cooling, and a sesame compound F consisting of partially touched porous agglomerates of sesame powder granules coated with fine powder is obtained. Obtained.

Next, the particles were crushed to a maximum particle size of 5 fl or less using a crusher (Morita Seisakusho, %c-3 type 3IP1) at 50 to 300 r.

p, m, transfer to a mixer with main mixing rotation, tap water 7,
000 Zheng (100 tons of Mei Jin compound) 3,
5 parts by weight) of an aqueous medium was added and mixed for 10 minutes to obtain a resin compound impregnated with an aqueous medium.

Install a 21 die in a 50m extruder, install 4 air knives on both sides of the die lip, and install 1 inch at the tip of the die lip, 170
°G++rl fat temperature tit 175℃), die lip 16
In step 1, use an air knife to quickly cool the dog, extend it and withdraw it, and take it out.
The above-mentioned aqueous medium impregnation treatment (grease-resistant concrete) was foamed and extruded to create a corrugated foam area and an IQ shape.

This resin base foam made from an aqueous medium is stretched into a corrugated foam sheet and has a directional closed cell structure, with a foam diameter of 0.8 m or less, often around 0.5 tIm diameter.
It's a bubble, Tsuya bubble'r1! The i ratio (volume magnification) was 16 times.

This O6 foam sheet was suitable as a cushioning material with soft foam.

Example blending amount l History y Resin Niacrylic-butatsuene-styrene copolymer dimmer (manufactured by Japan Synthetic Rubber Co., Ltd. JSjl ABS85. Specific gravity = = 1.05, MI = L11 10,000 Fine powder dual quality calcium carbonate (Shiraishi calcium) Whiten SB (manufactured by Kawaken Fine Chemicals Co., Ltd.; average particle size 1.8μ) He000 wood flour (dried fine powder, particle size 1ooA4/S pass) 500 Surface Y occupancy agent: Fatty acid alkanolamide (manufactured by Kawaken Fine Chemical Co., Ltd. -R Mitsu'-R1ijJE l
l 50 fatty acid amide (day 4), oil (Alflo P-1 (1) manufactured by Hachisha Co., Ltd.) 50 glycerin 100 Colorant: Ceramics Elo-100 Antioxidant: Distearylnaoprobionate 10 2.6-tert-butyl roof Resol IO Example 1
Using the same high speed mixer as above, the entire formulation was charged and mixed at high speed.

Approximately 11.8 minutes j4 i (after ω, the mixing motor current fluctuates wildly and begins to increase slightly (mixture wet at 220°C) 160 seconds 11
After the temperature passed, the temperature rose rapidly and reached 5OA (mixing/nose temperature 240°C) in 20 to 25 seconds (total of 180 to 18 samples), so the outlet was opened and the mixture was discharged.

The discharged mixed barrier is rapidly cooled and coarsely crushed by a low-speed rotating mixer with strong air cooling, resulting in a partially fused porous agglomerate of finely powdered resin powder particles with a maximum particle size of 5III.
Grind to 50 to 300 r.

P, m, transfer to a mixer with mixing rotation, and add polyoxyethylene fatty acid amine (Amit 308 manufactured by Kao Soap Co., Ltd.)
Ion exchange resin treated water containing 1% (l 00
An aqueous medium of QC (Resin Con/Mid 25 East Soft Parts with 100 parts of heavy leaves) was added and mixed for more than 10 minutes to carry out an aqueous medium impregnation treatment. 1.)TNir:ff
There was a thud.

506m (Irregular (thick plate-like) metal on the 11th exit!iIJ・
The cooling cysong die was installed using a device with a take-off machine, and the maximum temperature of the extrusion cylinder was 260°C and the die temperature was 210°C.

This aqueous medium formed a thick plate-like foam with a skin layer, a smooth firing surface, a closed cell structure, and a foaming ratio of 7.5 times at a foam diameter of fj O, 6 μμ. child.

This foam plank material is suitable for use as composite wood,
KA2 [sexually, ::4.

Center η (5 examples 4 Compounding amount y (manufactured by Misara Monsando Co., Ltd. Dai'I'7Vtsu'/SlII-516: MI=2.
2. Density = 1.051 10.000 Fine powder: Talc (
MS (manufactured by Nippon Talc Co., Ltd.; average particle size 9 μ), 3,000 starch (constarch, manufactured by Ryo Ito Co., Ltd.), 500 surfactant: monoethylene glycol, 50 alkylbenzene sulfonate (manufactured by Nippon Oil & Fats Co., Ltd.)
O Colorant: Titanium oxide [anatase type, A100 manufactured by 6 Hara Sangyo Co., Ltd.] 500 Antioxidant IF
, Agents: Solauryl thiodiglobionate 10 2.6-di-t-butyl Rufresol 10 Using the same high-speed mixer as in Example 1, add the ingredients other than the resin, rotate at high speed, and after 6 minutes, mix the resin. I put it in. After 21 minutes from the beginning, the mixing motor current started to fluctuate and increase slightly (mixture temperature + f2os℃), and after 120 seconds, it suddenly increased to 5~l.
O seconds (total 125-130 (yp l f 50 A
When the temperature reached 210° C., the discharge port was opened to discharge the mixture.

The raw mixture (r) was quickly cooled by a slow-rotating mixer with strong air cooling (roughly crushed and one resin powder particle damaged by fine powder was partially deposited at 1.?lt). A resin composition with porous agglomeration force was obtained.

Next, powder + i' + s (<Takeda Knee J 1'F tone Tc
-Type 3 Grinds to 50 to 300% large particle size at 3W.
00r.

Transfer to a mixing bowl with 100 m mixing rotation, add 100 ml of water and 5,000 ml of water.
cc (25 with 100 heavy weights of 4g fat Konnogland)
The aqueous medium (part 1) was added and mixed for 10 minutes to obtain a resin container treated with aqueous medium.

Equipment for obtaining a sheet using the same 70 fighter jet as in Example 1 - 4
So, extrusion cylinder maximum temperature +Q210℃, Gui convergence 19
0 °C (, +tt4 N temperature + r, (192 °C), die lip 180 °C
The resin foam made from this aqueous medium was smooth and had a closed-cell structure with thick walls, and the main part was chewy. This foam sheet was a homogeneous foam with a bubble diameter of 0.4 mm or less, and a foaming ratio (volume ratio) of 1005 times. This foam sheet was vacuum formed and pressure-formed and used for food containers such as trays. suitable.

Example 5 Blending amount: 9 g Resin: Ethylene-vinyl acetate copolymer (Yukalon Epa EVA2oF manufactured by Mitsubishi Yuka Co., Ltd.; MI = 2: 'M degree = 0.93) l (1,000
Fine powder: Kyoto quality calcium carbonate (Shiraishi Calcium Shaso Wheaton Ashi B; average particle size 1.8μ> 12.00
0. Nilupu powder (Ll, l Yokokusaku/Serpshahiro KC flock: W2O0; particle size 200M/S pass) 500 surfactant: Alkanolamide in fat (Kawaken Fine Chemical Company Amizole CDE) tsO
Fatty acid monoglyceroid (Rikemar S-100 manufactured by Riken Vitamin Co., Ltd.) 50 Calcium stearate (manufactured by Toa Silicification Co., Ltd.) 100 Colorant titanium dioxide (anatase type, Ishihara Sanresha, jIto A100) 500 Antioxidant: R Ntaeri Stolltetrakis (β-laurylthioglobione) 20 Hindered phenolic antioxidant 10 Example 1
Using the same high-speed mixing mixer as in the above, ingredients other than the resin were added, the mixer was rotated at high speed, and after 8 minutes, the resin was added. After 2 minutes from the beginning, the mixing current started to fluctuate and increase slightly (mixture temperature 185°C), and after 160 seconds it suddenly increased to 20~2
5 seconds (i ten tg.

After reaching 5OA (mixture temperature 195° C.) at 1B5 seconds), the outlet was opened and the mixture was discharged.

The discharged mixture is rapidly cooled and coarsely crushed by a low-speed rotating mixer with strong air cooling.
Morita Seisakusho Tc-, 343jP') with maximum particle size of 541
Grind to 50 to 300 r.

P, m, transferred to a mixer with mixing rotation, and heated molten water of 2% polyvinyl alcohol (manufactured by Kuraray Co., Ltd.) was passed through 6, (1
00cc (3 with resin compound of ion Toryobu)
ii) for 5 minutes after adding the aqueous medium of J mix,
The resin compound was impregnated with an aqueous medium.

A T-die is attached to a 50-order extruder, and before air knives are installed on both sides of the die lip, the tip of the die lip and the produced sheet are cooled and rolled up while being stretched. Temperature: 170℃ (resin temperature: 170℃)
), dicing rapidly with an air knife at 165°C, ・1
The resin compound' impregnated with an aqueous medium was foamed and extruded to form a corrugated foamed film.

The resin foam made from this aqueous medium is stretched into a corrugated foam sheet and has a directional closed-cell structure, and the foam diameter is homogeneous with a large diameter of 9.711111 or less, often around 0.5 qys, and a foaming ratio. (Body immersion magnification) was 5 times IL.

This foam sheet is flexible and elastic and is suitable as a cushioning material.

Procedural amendment (voluntary) June 13, 1980 Kazuo Wakasugi, Commissioner of the Patent Office1, Indication of the case: Patent Application No. 47028 of 1982, Title of the invention: Process for producing resin foam using an aqueous medium, 3. Relationship with the case of the person making the amendment Patent applicant address: 3-5-1 Miyaji, Konosu City, Saitama Name: Chuo Kagaku Co., Ltd. 4, Agent: 107 Address: 1-9-15-6 Akasaka, Minato-ku, Tokyo , Column 7 of "Detailed Description of the Invention" of the specification to be amended, content of the amendment as shown in the appendix (1) "r, etc." after "fever" on page 5, line 5 of the specification.
join.

(2) In the 4th line of page 6, the words ``Teru mo wa'' are corrected to ``Teru mo wa''.

(3) On page 6, lines 3 and 14, the words "acrylic" are corrected to "acrylonitrile."

(4) In the second line of page 9, the phrase ``1st prize is or'' is corrected to ``r, etc.''.

(5) In the second line of page 12, it says “Mononakerebo”.
Unless it's something," he corrected.

(6) On page 13, line 14, the word "Miki" is corrected to "Mixer."

(7) Delete "ma" at the end of the third line on page 16.

(8) Delete "sa" at the end of the 4th line on page 19.

(9) On page 23, line 3, the text [°dipropinate] is corrected to read "dipropionate."

(10) On page 23, line 13, the phrase "motor current" is corrected to "motor current."

(11) On page 24, lines 3-4, the phrase [resin combination made of porous aggregates] has been replaced with [fi made of porous aggregates].
I am corrected by saying, ``fatty compound 1nd''.

(12) On page 24, line 9, the text "1 Nurex" is corrected to "Newrex" and the text "5()00J" is corrected to "500J."

(13) On page 24, line 10, the text "2.5 folds with 1" is corrected to "2.5 folds".

(14) On page 27, lines 10-11, the phrase "cyclic neopentanetetrayl bis" is corrected to "dilauryl thiodipropionate."

(15) On page 28, line 1 of the same page, replace “motor current” with “
Correct it to "motor current."

(16) In the 8th line of page 28, the phrase "porous set" is corrected to "r porous set".

(17) On page 28, line 13, "7000ccJ is corrected to j700ccJ.

(18) On page 28, line 14 of the same page, the statement ``3.5 parts by weight'' is corrected to ``3.5 parts by weight.''

(19) On page 31, line 1.2, the phrase "1 motor current" is corrected to read "motor current."

(20) In the second line of page 32, ``Porous set J'' is corrected to ``porous set.''

(21) J 5 (1(') Oc
c Correct "J" to "r462cc" and "to" to "about".

(22) On page 33, line 11, "High impact polyethylene J" is corrected to "high impact polystyrene."

(23) On page 33, line 13, [Earflex I41
” has been corrected to read “Yearex ITJ.”

(24) On page 34, line 6, [Yurex H month is corrected to read ``Nylex January.

(25) On page 34, line 15, the phrase "1 motor current" is corrected to read "motor current."

(26) In the 5th line of page 35, the phrase "porous set" is corrected to "porous set".

(27) On page 35, line 9 of the same page, ``5.0(+(Correct the month to 1'338J.

(2S) On page 35, line 10, correct the phrase ``as 1'' to ``as about''.

(29) On page 38, line 8 of the same page, replace "motor current" with "
Correct it to "motor current."

(30) On page 38, line 15 of the same page, "Porous set J"
Porous set” is corrected.

(31) Page 39, line 4 snoring 6. old) (month and aru 6
75,” he corrected.

(32) On page 39, line 5 of the same document, the phrase "3 parts by weight" is corrected to "approximately 3 parts by weight."

that's all

Claims (1)

[Scope of Claims] (α) A thermoplastic resin powder and a hydrophilic substance that does not substantially melt at the melting temperature of the resin powder, which is partially embedded in an exposed state on the surface of the resin powder. A resin compound consisting of partially porous aggregates of thermoplastic resin powder coated with hydrophilic solid fine powder consisting of (b) melting and mixing the resin compound treated with the aqueous medium under pressurized conditions that substantially suppresses evaporation of the aqueous medium; (C) then melting. A method for producing a resin foam using an aqueous medium, which comprises foaming a kneaded resin composition by releasing it from a pressurized condition.