JPS60122766A - Flake-like cellulose sound-proofing heat insulator - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] In recent years, mechanical equipment, karaoke equipment, stereo equipment, pianos,
Regulations regarding noise emitted from guitars and various other sound sources have been tightened, and demands for soundproofing effects on the walls, floors, and ceilings of buildings are becoming stronger year by year. Furthermore, the demand for insulating buildings in order to save energy for cooling and heating is also becoming stronger. Flake cellulose sound and insulation materials obtained by crushing or defibrating aggregates of cellulose fibers such as paper and pulp are extremely suitable materials for soundproofing and thermally insulating these buildings, and have recently attracted attention from various quarters. It has been reached. However, flaky cellulose soundproofing and insulation materials, which are simply mechanically crushed or defibrated paper or pulp, inherit the combustibility and water absorption properties of the paper or pulp that is the raw material. There is. Although these characteristics may be actively utilized as a great advantage in some cases, in most cases they act as a great disadvantage when used as a building material. This is because flammability poses a risk of fire, while water absorbency poses a risk of deterioration if water or rain leaks.

These drawbacks of flaky cellulose acoustic insulation material that appear when manufactured without special considerations: Regarding the flammability of the core acoustic insulation material, boric acid, Water is added to known flame retardants used to make paper flame retardant, such as bur sand, ammonium sulfate, ammonium phosphorus, ammonium chloride, and guanidine sulfamate, to form a paste, dispersion, or solution. It is possible to impart combustibility to the soundproofing and insulating material by adding it during coarse crushing, refining, defibration, or in a separate blender, just as in the case of paper, and this problem has not been solved. ing. Water absorption, which is considered to be another drawback, can be solved by making the sound-insulating material hydrophobic by applying a hydrophobizing agent to the cellulose in the manufacturing process of the sound-insulating material, in a similar way to flame retardancy. Methods for this hydrophobization include wax emulsions, calcium stearate dispersions, alkyl ketene dimer dispersions, and styrene-acrylic aqueous ester emulsions. However, these methods are not necessarily suitable for producing flaky cellulose sound-insulating materials in terms of effectiveness and economy.

In general, the non-volatile components including the emulsifier for emulsion formation that remain after the moisture in the water repellent and sizing agent evaporates are flammable substances, and these flammable substances are contained in flaky cellulose sound and insulation materials. The presence of a large amount of is expected to have an adverse effect on imparting the above-mentioned flame retardant properties to the soundproofing and heat insulating material. As a result of investigating this point using a wax emulsion, as shown in Comparative Example 2, which will be described later, it was found that the flame retardant performance deteriorated as expected.

The present invention has overcome these difficulties, and has made it possible to produce a flaky cellulose soundproofing and heat-insulating material that has hydrophobicity at a low cost and has almost no effect on flame retardant performance. This is an extremely excellent method for producing soundproofing and heat insulating materials.

Hereinafter, the method for producing a flaky cellulose soundproofing and heat insulating material according to the present invention will be described in detail with reference to Examples and Comparative Examples.

In the present invention, pulp, paper, etc. can be used as the cellulose fibrous material.

Depending on the type of raw material, pulping method, presence or absence of a bleaching process, etc., the pulp may be bleached sulfite pulp (BSP), bleached hardwood kraft pulp (L-BKP), bleached softwood 2ft (N-
BKP), softwood unbleached kraft pulp (N-UKP)
), semi-chemical pulp (SEP), thermomechanical pulp (TMP), granton (GP), and other pulps, but the ten papers that can be used include newsprint and printing paper. , wrapping paper, paperboard, or waste paper thereof can be used.

Next, the hydrophobizing agent used in the present invention will be explained. Generally speaking, rough-in wax, microcrystalline wax, vegetable wax, etc. can be easily thought of as hydrophobizing agents. I think that the unsaturated oil is likely to be highly hydrophobic. As a result of experiments, it was found that by adding these materials when defibrating the cellulose fiber aggregates, the liquid ones can be added as they are, and the solid ones can be heated and molten to give them a certain degree of hydrophobicity. It was possible to obtain a flake-like acoustic insulation material. However, it is either impossible to produce flaky cellulose acoustic insulation materials with a high degree of hydrophobicity using these materials, or it is necessary to use extremely large amounts of these materials.

As mentioned at the beginning of the present invention, flaky cellulose sound and insulation materials are generally used that have been given flame retardant properties with a flame retardant. As a result, it does not have any negative effect on the flame retardant performance of the material, which is extremely inconvenient as a hydrophobizing agent used in the production of flake soundproofing and insulation materials, which are often required to be flame retardant due to their use. I have to say it.

As a result of repeated research and trial and error in order to overcome these drawbacks, the present inventor discovered that 17 alkenyl succinic anhydride is extremely compatible with the hydrophobizing agent used in the production of flaky cellulose soundproofing and insulation materials. I ended up doing it. Alkenyl succinic anhydride is shown in the chemical formula shown in Figure 1.
...A red-colored oily liquid that reacts with the hydroxyl groups present in cellulose to make it hydrophobic. This alkenyl succinic anhydride is applied directly to cellulose without using additional chemicals such as surfactants that may have a negative effect on flame retardant performance, resulting in the above-mentioned difficulties inherent in the manufacturing process of flaky cellulose soundproofing and insulation materials. It was confirmed that this problem could be overcome, and the present invention was achieved.

The method of adding alkenyl succinic anhydride to cellulose fibrous materials can be accomplished in a very simple manner.

That is, alkenyl succinic anhydride can be added alone, dispersed in water and added as a dispersion, or kneaded together with a flame retardant and water to form a paste when the cellulose fibrous material is crushed, refined or defibrated. The desired effect can be obtained by adding alkenyl succinic anhydride alone or in a dispersion with water, or by kneading it with a flame retardant and water to the defibrated flake cellulose sound and insulation material. The paste may be added and stirred. There is no need to use a surfactant or the like for dispersion in water; simply mixing and stirring is sufficient. If a surfactant is not used, it will separate into two layers in a few minutes to tens of minutes, but if it separates into two layers, it may be stirred again and added to the cellulose fibrous material.

However, when alkenyl succinic anhydride and water are mixed, the hydrophobizing ability is lost if left for a long time, so the dispersion or paste-like substance obtained by mixing alkenyl succinic anhydride and water should be prepared as soon as possible. Care must be taken when using it. The reason for this is thought to be that alkenyl succinic anhydride is hydrolyzed.

Hereinafter, examples and comparative examples will be shown and specifically explained.

In addition, 10 types from Example 1 to Example 10 and Example 1
20 A total of 11 types of prototypes were manufactured and 6 types of comparative products from Comparative Example 1 to Comparative Example 5 were manufactured using the lower part of a stainless steel cylindrical reactor with an inner diameter of 597 m and a depth of 565++ m equipped with a steam heating jacket. Two stirring blades were fixed in a cross shape and added to the rotating shaft, and the rotary mixer was constructed to rotate at 1,760 revolutions per minute.

Examples 11 and 12 have a diameter of 802 m and a width of 6 mm in an outer cylinder equipped with four fixed blades with a diameter of 648 mm and a thickness of 17 mm.
The cellulose fibrous material was only defibrated using a rotary crusher that rotates a 50 m cylindrical drum-shaped rotary blade, and a standard disintegrator for preparing a pulp dispersion as specified in JIS P 8209 was used. The chemicals were added and stirred. The defibrating machine that can be used in carrying out the present invention is not limited to the above-mentioned rotary mixer or rotary pulverizer, but also a defibrating machine having a defibrating mechanism different from the above-mentioned double furnace machine, such as a bottle mill, etc. The same can be done.

Example 1 Used newspaper air drying 8. Put the legs into a rotary mixer and coarsely crush them. Two minutes after the addition, when some of the old newspapers have broken down, add 20 f of alkenyl cono-phosphoric anhydride (product name: Fiveran 68, manufacturer: Oji National Co., Ltd.) to 1 part of water.
A dispersion of alkyunylcono-phosphoric anhydride, which had been mixed and stirred at 50 V, was slowly charged into the rotary mixer and further pulverized and defibrated for 5 minutes to obtain a flaky cellulose sound-insulating material.

Example 2 8Kf of air-dried old newspaper was put into a rotary mixer and coarsely crushed. 21 minutes after the addition, when the old newspapers had been crushed to some extent, 150 f of water was added to the mixed powder of 5 oot of #1 boric acid and 800 f of sand, mixed to form a paste into the rotary mixer. The mixture was stirred and defibrated. After stirring and defibrating for 2 minutes, alknylsuccinic anhydride (trade name)
Five Run 68 Manufacturer: Oji National Co., Ltd.)
20 f into the rotary mixer and further IC5
The mixture was stirred and defibrated for a minute to obtain a flaky cellulose sound-insulating material.

Comparative Example 1 Wax emulsion (trade name: Carbomul OD) was used instead of alkenyl succinic anhydride 202 in Example 2.
-G -160-A Manufacturer: Dick Vercules Co., Ltd.) A flaky cellulose soundproofing and heat-insulating material was obtained in the same manner as in Example 2 except that an amount equivalent to 4α52 of the dry nonvolatile content was put into the rotary mixer.

Comparative Example 2 Wax emulsion (trade name Carbomul 0
DG-160-A Manufacturer: Dick Vercules Co., Ltd.) A flaky cellulose soundproofing and heat-insulating material was obtained in the same manner as in Example 2, except that an amount equivalent to 200 f of dry non-volatile matter was put into a rotary mixer.

Comparative Example 8 Used newspaper to air-dry 8 to 4 in advance and use it as a steam jacket! l
) Pour into a rotary mixer heated to 105°C and coarsely crush. Throw it in! After 12 minutes, when the old newspaper had been crushed to some extent, 150 F of water was added to the mixed powder of 800 F of fluoric acid and 8002 #'i sand, mixed to form a paste, and the mixture was put into the rotary mixer. Then, pulverization and defibration were continued. Two minutes after adding the paste-like chemical, 400 f of heated and melted paraffin wax (product number: -PW 185°F, manufacturer: Ennstand Sekiyu Co., Ltd.) was added to the rotary mixer, and further pulverized and defibrated for 8 minutes.
A flaky cellulose sound and insulation material was obtained.

Example 8 Air-dried old newspapers 8~ are put into a rotary mixer and coarsely crushed. 2 minutes after the addition, when the old newspaper has become small pieces, add 1 part of water to a mixed powder of boric acid aooy and 800v of sand.
50F, alkenyl succinic anhydride (product name Sunsizer R8-168X manufacturer Sanyo Chemical Industries, Ltd.) 10
The mixture was added and mixed to form a paste, which was then put into the rotary mixer and further pulverized and defibrated for 5 minutes to obtain a flaky cellulose soundproofing and heat insulating material.

Example 4 Air-dried old cardboard paper 8V4 was put into a rotary mixer and crushed. 2 minutes after addition, goor acid.

Mixed powder of sand 8001, 1'50 f of water, alknylsuccinic anhydride (trade name Sunsizer R8-168)
X (manufacturer: Sanyo Chemical Industries, Ltd.) 202 was added and mixed to form a paste, which was put into the rotary mixer and continued to be coarsely crushed and defibrated for another 5 minutes to obtain a flaky cellulose soundproofing and heat insulating material.

Example 5 Unbleached ground pulp (unbleached GP) Air-dried 8 kg to 8 kg of water
After adding 00f, the moistened mixture was put into a rotary mixer and coarsely crushed. 1 minute after adding the pulp, add 250% ferric acid.
A mixed powder consisting of 450 tons of $15 sand and 200 tons of ammonium sulfate was placed in the rotary mixer, and coarse crushing and fibrillation were continued. After charging the powder, 20 f of alkynyl succinic anhydride (trade name: 7-I-Plan 68, manufacturer: Oji National Co., Ltd.) was charged into the rotary mixer, and after another 5 minutes, it was crushed and defibrated to obtain a flaky cellulose sound-insulating material. I got it.

Example 6 Hardwood bleached kraft pulp (L-BKP) Jt dry 8
Pour all kg into a rotary mixer and crush. Guanidine sulfamate (Product name: Avinon, Manufacturer: Sanwa Chemicals Co., Ltd.) 800 minutes from the injection of the nuclear valve
F[Water soot is added and mixed to form a paste, which is then put into the rotary mixer to continue pulverization and defibration. One minute after adding the 7-amino acid guanidine, alkenyl succinic anhydride (trade name: Fiveran 68, manufacturer: Oji National Co., Ltd.) 202 was added to the rotary mixer and pulverized and defibrated for another 5 minutes to form 7-lake cellulose. Soundproofing insulation material is 10.

Example 7 800 f of water was added to air-dried 8 Kf of colored wood-free waste paper to moisten it, and the resulting mixture was put into a rotary mixer and coarsely crushed.

One minute after adding the colored waste paper, when the complexion-colored waste paper turned into small pieces, 250r of boric acid and 460f of sand were added.
, a mixed powder consisting of 20Of secondary ammonium phosphorus was introduced into the rotary mixer and continued to be coarsely crushed and defibrated.

One minute after adding the mixed powder, alkenyl succinic anhydride (
Product name: Sunsizer R3-168 I got the material.

Example 8 Example? silicic anhydride in place of phosphoric anhydride)
In the same manner as in Example 7 except that ll ram 200 was used,
A flaky cellulose soundproofing material was obtained.

Example 9 A flaky cellulose soundproofing and heat-insulating material was obtained in the same manner as in Example 7, except that 200 t of ammonium chloride was used in place of the secondary ammonium phosphorus in Example 7.

Example 10 Used newspaper air-drying 601, defibrated into flakes using a pre-caulking rotary pulverizer, is charged into a standard disintegrator compliant with JIS P 820 and stirred.

This is combined with 61% boric acid. 62 pieces of sand, 8 pieces of water - no alkenyl
Hydrosuccinic acid (trade name: Sunsizer R8-168X, manufacturer: Sanyo Chemical Industries, Ltd.) α4- was mixed in a mortar and made into a paste and then added.

However, in this case, the standard disintegrator has small blades that have weak stirring power for flaky old newspaper, so it is necessary to use a cardboard spatula to push the flaky old newspaper toward the blades. The mixture was stirred in this manner for 5 minutes to obtain a flaky cellulose sound-insulating material.

Example 11 Water added when creating the mixed paste in Example 10 8
A flaky cellulose soundproofing and heat-insulating material was obtained in the same manner as in Example 10, except that - was changed to 15 - of water and a mixed paste was prepared and added.

Example 12 8 kg of old newspaper air-dried was pre-swaged into a steam jacket.
The mixture was ground and stirred in a rotary mixer heated to 05°C. Two minutes after being added, some of the old newspapers were crushed and 1
At this point, 160 f of water was added to a mixed powder of 800 F of fluoric acid and 800 tons of sand, and the resulting paste was put into the rotary mixer and stirred and defibrated. 2
After stirring for a minute to defibrate, heat and melt paraffin wax (Product number E-PW 185° FIJ Manufacturer Enon Standard Sekiyu Co., Ltd.) 2009 VC alkenyl cono-phosphoric anhydride (Product name Fivelan 68 Manufacturer Oji National Co., Ltd.) 101 The mixed molten liquid was put into the rotary mixer and further stirred and defibrated for 8 minutes to obtain a flaky cellulose sound-insulating material.

Comparative Example 4 Flake-like cellulose was prepared in the same manner as in Example 12, except that 10 f of calcium stearate (analytical reagent, manufacturer: Wako Pure Chemical Industries, Ltd.) was added and dissolved in place of the alkenylcono-phosphoric anhydride 107 in Example 12. Obtained sound insulation.

Comparative Example 5 10 g of alkenyl succinic anhydride in Example 12! A flaky cellulose sound-insulating material was obtained in the same manner as in Example 12, except that 10 f of alkyl ketene dimer (trade name: Opel, manufacturer: Nippon Fine Chemical Co., Ltd.) was added and dissolved instead.

The flaky cellulose soundproofing and heat-insulating materials obtained in Example 12 and Comparative Examples 5 were tested for hydrophobicity and flame retardancy using the methods described below.

Hydrophobicity test method Sample α5t, which had been pre-caulked and heat treated in a hot air dryer at 105°C for minutes, was compressed to a size of 9 L2 using a syringe, and then floated horizontally in water to determine the state of water absorption and sedimentation after 72 hours. Observe and evaluate based on the criteria shown in Table 1.

Flame retardancy test method Sample pre-caulked and heat-treated in a hot air dryer at 105°C for approx. At this time, adjust the height of the sample so that the top of the flame of the alcohol lamp touches the bottom of the sample. After 10 seconds, the sample is removed from the flame and the degree of flame retardancy is evaluated based on the criteria shown in Table 2.

Table 1 Hydrophobicity Judgment Criteria Test results for hydrophobicity and flame retardancy are shown in Table 8-(A) to Table 8-(G).

In Example 1, since no flame retardant was added, naturally flame retardancy was not observed, but the degree of hydrophobicity was extremely high.

Table 2 Flame retardant Direct-rate fixed standard Example 2i1 Contains flame retardant, flame retardant,
It has both hydrophobic and hydrophobic properties.

There was almost no difference in hydrophobicity from Example 1, and it was confirmed that alkenyl anhydride and uccinic acid were hardly affected by the flame retardant made of ferric acid and silica.

Table 8-(4) Comparative Example 1 is the same as Example 2 except for the hydrophobizing agent, but
The efficacy of Carpomile 0D-G-16OA as a hydrophobizing agent is weak, and an amount equivalent to 4051, which is more than twice the amount of alkenyl succinic anhydride added as a nonvolatile component, is
Hydrophobicity was low. Carbo Mule 0D-G-160
Comparative Example 2, in which a considerable amount of non-volatile content of -A was added,
Although the degree of hydrophobicity improved slightly, it still fell short of Example 2.
Moreover, a decrease in flame retardancy was observed, and the cost required for hydrophobization in this case was more than 10 times higher than when alkenyl succinic anhydride was used. It is clear how excellent alkenyl succinic anhydride is as a hydrophobizing agent.

Table 8 (■) Table 8 (C) Table 8 (G) In Comparative Example 8, which used a large amount of molten paraffin wax, the flame retardance was poor and the degree of hydrophobicity was not very high. In side 8, the amount of alkenyl succinic anhydride added was reduced to half that of Examples 1 and 2, but even with this, a flaky cellulose sound-insulating material with strong hydrophobicity was obtained.

The six examples from Example 4 to Example 9 were carried out by changing the cellulose fibrous material, the flame retardant, the manufacturer of the alkenyl succinic anhydride, the addition rate and method of addition, etc. In the case of , a flaky cellulose sound and insulation material with strong hydrophobicity and flame retardancy was also obtained. From this, alkenyl succinic anhydride is not affected by flame retardants such as boric acid, #nausea, ammonium sulfate, ammonium phosphate, ammonium chloride, and guanidine sulfamate, and conversely, It was confirmed that it is possible to impart hydrophobic properties to cellulose fibrous materials without having a substantial negative effect on efficacy.

Furthermore, alkenyl succinic anhydrides are prepared from Example IO to Example 1.
As shown in the two examples leading up to 1, it is also possible to hydrophobize cellulose fiber particles that have been defibrated into flakes. However, it is not directly related to hydrophobization, but when trying to impart flame retardant properties to cellulose fibrous material that has been defibrated into flakes, it is recommended to add a flame retardant at the same time as defibration. In comparison, when the amount of flame retardant was the same, it was not possible to impart the same level of flame retardant performance as when the flame retardant was added at the same time as fibrillation unless the amount of added water was increased. Example 1° and Example 11 compare this relationship.

Example 12 and Comparative Example 4,5ti Alkenyl succinic anhydride, calcium stearate, and alkylketenta "imer" are shown to show the effects when used in combination with molten paraffin.As is clear from these results, alkylketenta "imer" Imer and calcium stearate had very weak hydrophobizing ability, whereas alkenyl succinic anhydride showed strong hydrophobic and hydrating ability.

[Brief explanation of the drawing]

FIG. 1 shows the chemical structural formula of alkenylsuccinic anhydride. However, R is an alkyl group, C is a carbon atom, H
is a hydrogen atom, OFi is an oxygen atom, and n is an integer Patent applicant Kishu Paper Co., Ltd. Procedures Amendment Book Tono ′\1
Indication of the case Patent Application No. 228791 filed in 1980, title of the invention Flake-like cellulose soundproofing and heat-insulating material 3 Relationship with the case by the person making the amendment Patent applicant Furigazu Address (residence) 1-4-16 Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture
No. 4 Date of amendment order February 28, 1980 5 Subject of amendment Full text of application and specification 6 Contents of amendment Engraving of application and specification (no change in content)

Claims (3)

[Claims] (1) A flaky cellulose sound-insulating material characterized by using alkenyl succinic anhydride as a hydrophobizing agent. (2) A flaky cellulose sound-insulating material characterized by adding alkenyl succinic anhydride to a cellulose fiber aggregate and defibrating it. (3) A flaky cellulose sound-insulating material characterized by adding alkenyl succinic anhydride to a cellulose fiber material that has been defibrated into flakes and mixing and stirring the mixture.