WO1993009168A1

WO1993009168A1 - Rigid inorganic-filled foam and production thereof

Info

Publication number: WO1993009168A1
Application number: PCT/JP1992/001427
Authority: WO
Inventors: Yuji Hiratsuka; Yoshihiro Kimura; Takayuki Nagayoshi; Mitsuhiro Kasai
Original assignee: Kanegafuchi Kagaku Kogyo Kabushiki Kaisha
Priority date: 1991-11-08
Filing date: 1992-11-04
Publication date: 1993-05-13

Abstract

A rigid foam produced by expanding a foaming composition comprising (A) a vinyl chloride/vinyl acetate copolymer, prepared by the polymerization using an alkylbenzenesulfonic acid salt as an emulsifier and having an average degree of polymerization of 1,500 to 5,000 and a vinyl acetate content of 3-20 wt.%, (B) an inorganic material containing inorganic particles and inorganic fibers with a diameter of 1 νm or above, (C) a water-insoluble solvent, and (D) a decomposable blowing agent. This foam has excellent burning characteristics, a high closed cell content and a large expansion ratio, and hence is excellent in heat insulation performance and water absorption resistance.

Description

Akira Itoda Inorganic-filled rigid foam and its manufacturing technology

The present invention relates to an inorganic-filled rigid foam and a method for producing the same. For details,】 1 SA 1Π1 passed the flame retardant class 1 in the surface test specified in the “flame retardancy test method for inner layer materials and building method of buildings” and closed cells. The present invention relates to an inorganic-filled rigid foam having a high expansion ratio, a high expansion ratio, that is, both of a heat insulating property and a non-water-absorbing property, and a method of producing the same. Background technique # 1

Conventionally, as an expandable composition for filling a vinyl resin-based resin foam filled with an inorganic substance and a hard foam comprising the same, for example, an internationally disclosed 89/09 "No. 6 Pan fret

(1989), JP-A-63-85071, JP-B-62-513, and the like are known.

The international publication c. Rigid foams made of the foamable composition described in the fretlets use a specific solvent that is compatible with vinyl chloride resin (hereinafter referred to as PVC). As a result, it dissolves PVC to molecular weight, and covers the surface of inorganic substances such as rock wool with a PVC film, and has a high closed cell ratio and high foaming ratio. It is a good foam. As a solvent with good compatibility with P, a water-soluble solvent such as acetone, hexanone, methyl ethyl ketone, etc. When using water, the use of non-water-soluble solvents may be necessary because extra costs may be required for the solvent recovery equipment. In addition, the appearance of a foam having the above-mentioned properties has been desired. In the invention described in the above-mentioned publication, in order to fill and disperse a large amount of an inorganic substance, generally, the energy required for radical decomposition as a cross-linking agent is 35 kcal / ni () l. It is necessary to use a combination of the above, such as dicumyl peroxide and tert-butyl cumyl peroxide, but this is not the case. In some cases, the use of metal had adverse effects on combustion characteristics. In addition, there are several problems with industrial-scale production, such as the need to use limited kneading equipment to mix and disperse large amounts of inorganic substances. Was.

In addition, in the invention described in the above-mentioned publication, the foaming group is used.When a water-insoluble solvent such as toluene is used for the composition, the water-insoluble solvent such as toluene is used for the PVC. Is difficult to dissolve, so that even if the foam can be filled, the closed cell ratio is small and the water absorption is only ^2.5 g / 10 (m2) As a result, there was a problem in that the non-water absorption deteriorated, and the foam accumulated water over a long period of use, and its heat insulating property was sometimes reduced.

The present invention has been made in view of the above circumstances, and is insoluble in water, has low toxicity, and is inexpensive. Regardless of which water-soluble solvent that satisfies any condition, it is possible to produce a foam with high closed cell ratio and high expansion ratio because of its excellent combustion characteristics. O

That is, according to the present invention, the water absorption amount is excellent in the heat insulating property.

0.1 L Og / 100 cm ² or less, non-water-absorbing, maintains high heat insulation for a long period of time, and further combusts to prevent combustion collapse Inorganic-filled rigid foam with excellent properties The purpose of the present invention is to provide a method for producing the same.

The present invention is based on (1) (A) polymerization using an alkylbenzensulfonate as an emulsifier, and having a vinyl nitrate content of 3 to 2 Q% by weight. Certain vinyl chloride-vinyl acetate copolymers, (B) inorganic particulates and inorganics containing inorganic fibers with a diameter of 1 m or more, (C) water-insoluble solvents and) Inorganic-filled hard foam obtained by foaming a foaming composition comprising a foaming agent, and (A) anoloxybenzensulfonate as an emulsifier And vinyl alcohol sulphate copolymer having a vinyl sulphate content of 3 to 2β% by weight, (ii) inorganic particulate matter and a diameter of 1%. / m or more, and a foamable composition comprising (C) a water-insoluble solvent and (D) a decomposable foaming agent. The kneaded vinyl acetate copolymer and the water-insoluble solvent are kneaded at a temperature not lower than the temperature at which they are compatible with each other, and foamed after being pressurized in a temperature range suitable for the decomposition of the decomposable foaming agent. A method for producing an inorganic-filled rigid foam, characterized by cooling to an appropriate temperature and defoaming to cause foaming, and then heating to evaporate and remove the solvent, and ③. (A) Alkalibenzensulfonate is used as an emulsifier and polymerized to give a vinyl chloride content of 3 to 20% by weight. Vinylic acid acid vinyl copolymer, (B) inorganic particulate matter and inorganic matter containing inorganic fiber with a diameter of 1 / ID or more, (C) water-insoluble solvent and (D) degradable type The foaming composition comprising a foaming agent is compatible with the vinyl chloride vinyl acetate copolymer and the water-soluble solvent. Kneading at a temperature higher than the temperature to be exhibited and decomposition foaming After pressurizing in a temperature range suitable for the decomposition of the agent, it is cooled to the appropriate foaming temperature, depressurized and foamed, and then the steam is brought into direct contact with the foam obtained. The present invention relates to a method for producing an inorganic-filled hard foam, which is characterized in that the foam is formed into a foam and then the solvent is volatilized and removed by heating. BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides a rigid foam of a vinyl chloride resin, which has a tendency to have a lower compatibility with a resin than a water-soluble solvent. This invention allows the use of a water-soluble solvent, and uses a special grade of vinyl chloride-vinyl acetate copolymer at a temperature at which this is compatible with the water-insoluble solvent. A hard foam having a high closed cell ratio and a high expansion ratio can be kneaded as described above, even if it is filled with an inorganic material containing inorganic fibers having a diameter of at least. It has been completed based on the results obtained.

The technology for producing inorganic-filled rigid foams containing inorganic fibers with a diameter of 1 / im or more using a water-insoluble solvent is based on vinyl chloride-vinyl acid copolymer which is compatible with the water-insoluble solvent. It has been completed for the first time by the present invention, which makes use of merging.

Here, the temperature at which the above-mentioned vinyl chloride-vinyl acid copolymer and the water-insoluble solvent exhibit compatibility is defined as the temperature at which the vinyl chloride-vinyl succinate copolymer and the inorganic solvent are used. The temperature at which the mixture shows syrup-like viscosity when the mixture consisting of inorganic materials including fibers is kneaded while increasing the temperature from room temperature at an arbitrary kneading speed using an arbitrary kneading machine. The temperature varies depending on the type of each raw material, kneading conditions, etc.

Conventionally, a specific solvent that exhibits PVC solubility with water, that is, water The use of a soluble polar solvent has enabled the foaming of an expandable composition containing inorganic fibers, but the use of a special grade of vinyl chloride vinyl acetate When a water-insoluble solvent is used, a closed cell ratio is high and an inorganic filler with a high expansion ratio is used, even when a water-insoluble solvent is used. It is now possible to produce hard foam.

The vinyl chloride / acid vinyl copolymer refers to a resin obtained by copolymerizing vinyl chloride and vinyl nitrate, and includes a random copolymer and a block copolymer. It does not matter whether the copolymer is any of the graphite copolymer and the graphite copolymer. Also, in order to increase the solubility with toluene, for example, vinyl chloride-vinyl acetate copolymers are produced by emulsion polymerization, micro-suspension polymerization, etc. It is desired to be a so-called paste resin. As an emulsifier used during polymerization, dodecinolene benzene is used to prevent cracking of the obtained rigid foam during combustion. Anorexylbenzensulfonate represented by sodium phosphate, etc. is used.

The vinyl acetate content in the vinyl chloride-vinyl acetate copolymer is usually 3 to 20% by weight, preferably 3 to 15% by weight, and more preferably 3 to 8% by weight. % By weight. When the content of vinyl acetate is less than 3% by weight, the compatibility between the vinyl chloride-vinyl acetate copolymer and the water-insoluble solvent is reduced, resulting in good foaming. When the body becomes difficult to obtain and exceeds 20% by weight, the viscosity of the foamable composition is too low, so that the suitable temperature for foaming is lowered and industrial Productivity starts to deteriorate.

The vinyl chloride-vinyl acetate copolymer is a relatively large flat material different from a general-purpose vinyl chloride-vinyl acetate copolymer. Special ones having a degree of homopolymerization are particularly preferred in the present invention. The average degree of polymerization of such a vinyl chloride-vinyl acetate copolymer is determined in accordance with the specific viscosity measurement method described in “Test method for vinyl chloride resin”. 0 to 500, preferably 180 (preferably! To 4Q00. If the weight is less than 15Q0, foam At times, the cell membrane tends to be difficult to withstand the gas pressure of the foaming agent, so that the closed cell rate tends to decrease and the foaming ratio is high. If the amount exceeds 50,000, a rigid foam having a high expansion ratio can be obtained unless a large amount of a decomposable foaming agent is used. It tends to be less prone to industrial and cost-effective manufacturing disadvantages.

In addition, as long as the above conditions are satisfied and the object of the present invention is not impaired, the other copolymer is also combined with the vinyl chloride vinyl acetate copolymer. You can use it for

In the present invention, inorganic particulates and inorganic fibers having a diameter of 1 #m or more are used in combination in order to enhance the combustion characteristics.

The inorganic fiber having a diameter of 1 μππ or more does not include asbestos having a diameter of about 0.1 mm to 0.1 ^ ffl, which is considered to be unfavorable for health. Cotton, glass fiber, ceramic fiber, aluminum fiber, carbon fiber, quartz fiber, borane fiber, various metal fibers, various whiskers, etc. These inorganic outfits may be used alone or in combination of two or more. Among these inorganic fibers, rock wool is particularly preferred because of its foam-forming stiffness, the physical properties of the resulting rigid foam, and its cost.

As for the fiber length of the inorganic fiber used in the present invention, the longer the fiber length, the greater the effect of filling the rigid foam, while the shorter the fiber length. 10 m to 50 mm, preferably 20 D, because the filling efficiency is good. ~ 20 mm, preferably 30 // m ~ 1 O mm, preferably 0

The amount of the inorganic fiber to be used is appropriately adjusted according to the burning characteristics of the obtained rigid foam, but is usually relative to 100 parts by weight of vinyl chloride-vinyl acetate copolymer. 22 to 22,000 parts by weight, preferably 10 to 10 G parts by weight, more preferably 15 to? 0 parts by weight. As long as the amount of non-woven fiber used is less than 2 parts by weight, the obtained rigid foam will have cracking, shrinkage, etc., and have good combustion characteristics. There is a tendency for it to be difficult to feed the water, and if the weight exceeds 200 parts by weight, the rigid foam cell membrane contains There is a tendency for the rigid foam to have a small tendency to be closed, have a high closed cell rate, and have a high expansion ratio, so that it tends to be hard to obtain.

As the inorganic particles, those having an average particle diameter of about 0.01 to 300 βm are used, and there is no particular limitation on the type. Specific examples of such inorganic particulate matter include, for example, My power, evening water, potassium, calcium carbonate, aluminum hydroxide, and the like. Zinc compounds such as metal hydroxides and zinc oxide are extinguished, and in addition to these, hollow bodies such as silica and lanthanum, and zeolite Porous materials such as activated carbon can also be used. O Among them, from the viewpoint of price and availability, sunset, carbonated carbon dioxide, etc. Preference is given to calcium and the like, and metal hydroxides such as aluminum hydroxide and zinc compounds such as zinc oxide are preferred from the viewpoint of improving combustion characteristics. Good

In the present invention, in order to improve the rectangularity and flatness of the obtained rigid foam, inorganic hard particles are used. It is preferable to use flaky inorganic particles having a peak ratio of 2 or more.

The above-mentioned aspect ratio refers to a value of a ratio between an average particle diameter of the inorganic particulate matter and a thickness of the inorganic particulate matter. Here, the average particle size is calculated by calculating the stalks diameter by a light transmission measurement method, and calculating the weight ratio occupied by the stalks diameter and the stalks diameter. It is measured and integrated from the smaller particle diameter to obtain the stokes diameter at 50% by weight of the total weight. For the classification of particles, the natural sedimentation method is used for particles with a particle diameter of more than 5 / im, and the centrifugal separation method is used for particles not exceeding 5 m. Was.

When the aspect ratio of the above-mentioned flake-shaped inorganic particulate matter is less than 2, there is a problem that the effect of improving the target rectangularity and flattening rate is reduced. is there . When the flake-like inorganic particles have an excessively large aspect ratio, cavities are likely to be formed in the obtained rigid foam. Therefore, the aspect ratio is desirably 200 or less, preferably 3 to 150.

There is no particular limitation on the average particle diameter and the thickness of the flaky inorganic particles, and the average particle diameter is usually about 0.01 to 300 μm, and the thickness is about 0. It is preferable that the length is about 0.05 to 150 m.

Representative examples of the flaky inorganic particulate material having an aspect ratio of 2 or more include, for example, kaolin, cray, and tanole mymi force. It is terrible.

The scaly inorganic particles having an aspect ratio of 2 or more can be used by replacing a part or all of the inorganic particles. In order to improve the rectangular ratio and the flattening ratio, The amount of the scaly inorganic particles having an aspect ratio of 2 or more is preferably 15 parts or more with respect to 100 parts by weight of vinyl chloride-vinyl acetate copolymer. Should be at least 20 parts by weight, and more preferably at least 50 parts by weight.

In the present invention, when a scale / particle having an aspect ratio of 2 or more is used as the inorganic particle, the rectangular ratio and the flatness of the obtained rigid foam are obtained. The reason for the increase in the porosity is not certain, but it is likely that the flaky inorganic particles improve the viscosity of the foamable composition alone, thereby increasing the foaming time. It is presumed to be based on the tendency of the shape to be lost o

The amount of the inorganic particles used is appropriately adjusted according to the ease of foaming and combustion characteristics, but is usually 100 parts by weight of vinyl chloride vinyl acetate copolymer. To 900 parts by weight, preferably 300 to 800 parts by weight, and more preferably 0 to 100 parts by weight.

It should be adjusted to be 100 parts by weight.

In addition, the amount of the inorganic material containing fe-free materials and inorganic fibers having a diameter of 1 nm or more was 9 parts by weight based on 100 parts by weight of vinyl chloride-vinyl acetate copolymer. It is adjusted to be 5 to 950 parts by weight, preferably 310 to 900 parts by weight, and more preferably 415 to 750 parts by weight. This is what you want. As long as the amount of the inorganic substance used is less than about sci $ Q, it does not pass the first class of flame retardant in the table ffl test specified in J1SA1332. If the temperature exceeds the above range, it is not possible to expect further flame-retardant properties, and the cost tends to be rather high. No.

In the present invention, the hard foam obtained when scale-like inorganic granules having an aspect ratio of 2 or more is used is used. Cavities tend to form easily in the body. This is because, in the case where the flaky inorganic particles were used, there were many contact interfaces between the flaky inorganic particles and the vinyl chloride-vinyl acetate copolymer in the cell membrane at the time of foaming. Therefore, the interface is likely to be stressed by the pressure in the cell at the time of foaming, and the cell membrane is liable to be broken by the stress. It is considered that

Therefore, in order to prevent the cell membrane from being broken by such stress, it is necessary to use acrylic acid ester and / or Z or methacrylic acid. Compounds having two or more ester groups (hereinafter sometimes referred to as (meth) acrylic acid ester groups) (hereinafter simply referred to as (meth) acrylic acid esters) It is preferable to use a tel.

When the (meth) acrylic acid ester is used, the decomposition-type foaming agent contained in the foamable composition may be used to produce a vinyl chloride vinyl chloride copolymer. The (meth) acrylic acid ester is polymerized in the cell, and the spinning property of the cell membrane during foaming

It is thought that by supporting (sppinnabili), the cell membrane is prevented from being broken by scaly inorganic particles.

Specific examples of the (meth) acrylic acid ester include, for example, triethylene glycol having an alkylenoxide in the main chain. (Meta) Clear rate, 1,3-butyrene recall (meta) Accelerate, polyethylene recall (meta) Trimethylolprono with alkyl group in the main chain, ⁰ -tri (meta) acrylate; Alcohol group in the main chain 1,9-Non-George (meta) clear, 1,6-Hexane-George (meta) The crelets and the like may be used alone or in combination of two or more. Among these (meth) acrylic acid esters, in order to improve the foaming ratio of the obtained rigid foam, acrylic acid is used. The ester group

The acrylate ester compound having 2 or more is preferred. 0 Description (Member) The molecular weight of the acrylate ester depends on the dispersibility in the foamable composition. Considering the spinnability and spinnability, Π 2 ~

It is preferable that the value be 500, especially 200 to 400. o Note: The amount of acrylic acid ester used is ) In order to give the effect of blending acrylic acid ester, use flake-shaped inorganic granules with an aspect ratio of 2 or more. In order to prevent the formation of voids in the rigid foam which may occur when the reaction is carried out, it is necessary to use 100 parts by weight of vinyl chloride / vinyl acetate copolymer. It is preferable to use at least 2 parts by weight, especially at least 5 parts by weight, but even more, the amount of the acrylic acid ester used is very high. If there is too much, the viscosity of the foamable compound alone will be reduced, and the rectangularity and flatness of the obtained rigid foam will tend to be insignificant. salt It is preferred that the amount be not more than 20 parts by weight, especially not more than 15 parts by weight, based on 100 parts by weight of the vinyl chloride-vinyl acetate copolymer.

The water-insoluble solvent as used herein refers to a solvent in which the weight of water dissolved in 2 C with respect to the weight of the solvent (100 g) is lg or less. In general, it is preferably 0.5 g or less, more preferably 0.1 g or less.

刖 Specific examples of the water-insoluble solvent include, for example, benzene, toluene, xylene, and monocyclo benzene. Of these, vinyl chloride-vinyl nitrate From the viewpoints of compatibility with the copolymer, economy and safety to the human body, toluene and xylene are preferred. These water-insoluble solvents are usually used alone or in combination of two or more.

The amount of the water-insoluble solvent used depends on the average degree of polymerization of the vinyl chloride-vinyl acetate copolymer and the amount of the inorganic substance used, but is usually 100 parts by weight of the vinyl chloride-vinyl acetate copolymer. It is desirable that the amount be 100 to 700 parts by weight, preferably 200 to 5 parts by weight. The amount of the water-insoluble solvent used is 1 part by weight of the vinyl chloride-vinyl acetate copolymer.

For less than 100 parts by weight, hard foams with high expansion ratios tend to be difficult to obtain, and for more than 700 parts by weight. In some cases, the suitable foaming temperature is lower than room temperature, which makes production on an industrial scale difficult, and it is difficult to obtain a good rigid foam. There is a tendency.

Examples of the decomposable foaming agent include azodicarbon amide, azobisisobutyronitrile, 2,2-azozobis (2-methyl) Noleptilonitrile), ziazomino benzene, Ν, Ν'- ginitorosopenta methylentetramin, ト -toluenesurho Nylhydrazide, 1-phenyl-5-mercapto-1Η--Trazol, and other substances that generate nitrogen gas by thermal decomposition It is said that it is preferred. In the present invention, a decomposition-type blowing agent that generates nitrogen gas is preferably used because the nitrogen gas volatilizes and removes a water-insoluble solvent such as toluene during foaming. This is because, in the process, the hard foam does not easily dissipate through the hard foam, so that defects such as shrinkage of the hard foam hardly occur. In the present invention, when the (meth) acrylic acid ester is used, as described above, the decomposition-type foaming agent comprises (Meta) Acts as a polymerization initiator for acrylic acid ester.

The amount of the decomposed foaming agent used depends on the desired expansion ratio, the type of the decomposed foaming agent, the type and amount of the inorganic substance, the type of the water-insoluble solvent, and the amount used. Usually, the amount is 5 to 100 parts by weight, preferably 1 (! To 50 parts by weight) per 10 G parts by weight of the vinyl chloride-vinyl acetate copolymer. If the amount of the decomposable foaming agent used is less than 5 parts by weight, a rigid foam having a desired expansion ratio may not be obtained. If the amount exceeds 100 parts by weight, the cell membrane is likely to break during foaming, and the closed cell ratio can be maintained at a high level. It tends to disappear.

The decomposable foaming agent also functions as a polymerization initiator of the (meth) acrylic acid ester, but the decomposable foaming agent for producing a foam is used. It does not need to be increased particularly for the quantity to be sufficiently large.

In the present invention, various stabilizers can be used. As such a stabilizer, the ability to inhibit the decomposition and degradation of a vinyl chloride-vinyl acetate copolymer can be used. Those with are particularly preferred. Specific examples of the stabilizer include, for example, dibasic lead stearate, dibasic lead phosphite, tribasic lead sulfate, zinc stearate, and stearate. Calcium phosphate, Magnesium stearate, Zinc octylate, Dibutyltin distearate, Dibutylzylzillau These stabilizers may be used alone or in combination of two or more. The amount of the stabilizer used is the same for both vinyl chloride and vinyl acetate. The amount is usually 1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on the polymer {β} part by weight. If the amount of the stabilizer used is less than 1 part by weight, the effect of adding the stabilizer may be lacking, or 2 (if the amount exceeds 1 part by weight, From the viewpoint of the stabilizing effect, the further improvement in the effect is small, and on the contrary, it is disadvantageous in terms of cost.

In the present invention, the foamable composition further includes, for example, various antioxidants, ultraviolet absorbers, pigments such as titanium oxide and ultramarine blue, tertiary amine, and alkyl sulfo. It is commonly used as an additive in plastics such as antistatic agents such as phosphates, nucleating agents such as D-mannitol, dipentyl erythritol, etc. It can be used by adjusting it as needed.

Next, an example of the method for producing the foamable composition according to the present invention will be described.

First, a raw material measured in a predetermined amount is put into a kneading machine such as a double-arm kneader. Until the raw materials are uniformly dispersed, the temperature of the water-insoluble solvent is higher than the temperature at which the water-soluble solvent is compatible with the vinyl chloride-vinyl acetate copolymer and lower than the boiling point of the water-insoluble solvent, for example, If it is luene, knead it at a temperature of about 110, and if necessary, lower the temperature of the mixture once and add a decomposable blowing agent until it is evenly dispersed. To

If the water-insoluble solvent is kneaded at a temperature not lower than the temperature at which it is compatible with the vinyl chloride-vinyl acetate copolymer and at a temperature not higher than the boiling point of the water-insoluble solvent, the type of the kneader is particularly suitable. There is no limitation.

Manufactures rigid foams from foam compositions that are tailored Explain how to do this.

The foamable composition is filled in a hermetically sealing mold made of, for example, an aluminum alloy, and the mold is made of, for example, an oil-pressure driven multi-stage mold. The foamable composition is heated under pressure, for example, by setting it on a press machine.

The pressure and heating conditions differ depending on the components of the foamable composition, but it is necessary that the decomposition of the decomposable foaming agent is substantially completed, and the The appropriate suitable temperature, specifically, the temperature suitable for the decomposition of the decomposable foaming agent, for example, when azobisisobutyrononitrile is used as the foaming agent. In practice, the temperature is about 100 to 160 ° C, and the pressure is selected to be about 140 to 300 kg / cm ² . When the temperature reaches a predetermined value, maintaining the temperature for about 1 to 30 minutes increases the temperature of the entire foaming composition in the mold as uniformly as possible. Preferred in point. After that, while the mold is pressurized, the temperature of the pressurized heating plate of the press machine is lowered to a suitable foaming temperature by using a cooling medium such as water. The appropriate temperature for foaming varies depending on the composition of the foamable composition, the shape of the mold and its dimensions, but it is usually lower than the above-mentioned heating temperature, and the cell film is foamed during foaming. The temperature at which the viscoelasticity of the vinyl chloride-vinyl acetate copolymer is such that the foamed gas does not escape due to the breakage is from 20 to It is about 10 D ° C. When the mold contents reach the foaming appropriate temperature, the mold is opened, and the mold contents are released under atmospheric pressure, whereby a foam is obtained.

Since the used solvent remains in the foam immediately after foaming, the foaming ratio can be further increased by directly contacting with steam as it is or as it is. Higher temperature, leave at an appropriate temperature appropriate for the solvent and for an appropriate time to evaporate and remove the remaining solvent. What The removal of the organic solvent from the foam can be promoted by cutting with a cutter or the like to increase the surface area.

If the foam is brought into direct contact with steam before volatilization and removal of the residual solvent, the foam surface is covered with moisture, and the volatilization of the water-insoluble solvent is delayed. Because the foam is heated in the step, the foam can be further foamed. Therefore, in this case, an economical advantage such as a reduction in the amount of the blowing agent can be obtained.

In this way, the following method can be used to directly contact the foam with steam before removing and removing the residual solvent. And can be done.

In other words, the foam obtained above is heated in the presence of moisture on the surface of the foam (hereinafter referred to as a primary foam), and the foam remaining in the cells of the primary foam is heated. The foam is expanded by increasing the gas pressure of the agent and the vapor pressure of the solvent. At this time,

By heating the foam in the presence of moisture on the surface of the primary foam and adjusting the surface temperature, the amount of expansion of the foam can be freely set. You. If the surface temperature of such a primary foam is too low, the vapor pressure of the solvent will decrease and the elastic strength of the cell membrane will increase, which will result in a decrease in the surface temperature. A rigid foam with a high expansion ratio, with a cell volume commensurate with it, will be difficult to obtain, and if it is too high, the amount of inorganic substances However, due to the presence of a large amount of solvent, the cell membrane tends to be drunk, and the foam tends to expand too much. 6 (! -95, preferably 65-90 ° C, more preferred) due to the lower strength of the material and the tendency to crack in the foam. Or 70 to 8 Q ° C. The heating time in the presence of moisture on the surface of the primary foam depends on the surface temperature of the primary foam, the desired expansion ratio, etc., so it must be determined unequivocally. I can't do it. Usually, the heating time is such that the heat is sufficiently transferred to the inside of the primary foam and the solvent is removed to such an extent that cracks do not occur in the drying process using the hot air. And a time sufficient for the mechanical strength of the cell membrane to be improved. In general, it is said that the time required for heat transfer and diffusion and transfer of a solvent are both proportional to the square of the thickness of the foam. Therefore, if it is a plate-like primary foam having a thickness of about 50 mm, for example, it is preferable that the time be 0.1 to 2 hours. However, if the heating time is too long, the amount of residual solvent in the obtained rigid foam will be small, and the next step, hot air Residual residue in the cell during the drying process. Since the vapor pressure of the agent may become too low and the inside of the rigid foam may contract due to the reduced pressure, set a proper time. It is hoped that it will be determined accordingly.

As a method of heating the surface of the primary foam in the presence of moisture, for example, spraying a steam having a predetermined temperature under a predetermined pressure on the primary foam To heat the water with the specified temperature in the form of a mist or shower to cover the surface of the primary foam and heat it. The primary foam can be placed in an air-conditioned environment and humidity, or the primary foam can be immersed in water at a predetermined temperature. In the present invention, other methods may be used as long as the surface temperature of the foam is uniform, the foam is uniformly heated, and moisture is uniformly present. The primary foam is heated by spraying a steam with a specified temperature. In the method of placing the primary foam in an atmosphere adjusted to a predetermined temperature and humidity, the primary foam is always wet and the latent heat is applied. To achieve this, it is preferred that the atmosphere around the primary foam be at a vapor pressure close to or saturated with moisture. Further, in the present invention, in order to prevent the solvent from volatilizing from the primary foam, moisture is to uniformly cover the entire surface of the primary foam. Is preferred.

By heating for a predetermined time in the presence of moisture on the surface of the primary foam, the gas pressure of the residual foaming agent and the vapor pressure of the residual solvent in the cells of the primary foam are increased. The hard foam obtained by further foaming is subjected to a treatment such as hot-air drying in which hot air is brought into contact with the foam, for example, to remove the solvent. .

When hot air drying is performed, the solvent is removed from the rigid foam, the cell membrane is solidified, and the solvent gas in the cell is replaced with air. If the replacement of the solvent gas by air is insufficient, the solvent will condense in the foam during cooling of the rigid foam and the foam will shrink due to negative pressure in the cell This will be.

The hot air temperature during hot air drying may vary depending on the type of solvent and the amount remaining in the rigid foam if the temperature is too high. If the amount of residual solvent is relatively large, the foam expands again during hot-air drying, and its expansion exceeds the allowable expansion of the cell membrane, causing cracks inside the foam. In some cases, the vinyl chloride-monovinyl acid copolymer is deteriorated or discolored. Also, if the temperature of the hot air is too low, the internal pressure of the During drying, the pressure is reduced and may shrink. As a result, the temperature of the hot air should be higher than the temperature at which the primary foam is heated, at least in the presence of moisture.

The drying time when hot air drying is performed is usually such that the solvent is removed to such an extent that the quality of the foam is not adversely affected by the residual solvent in the foam, and the drying is carried out to the foam. The time during which the air is diffused is chosen. The drying time is the same as when the primary foam is heated in the presence of moisture on the surface, and the vapor of the residual solvent and the transfer of the residual foam gas present in the foam are the same as when the primary foam is heated. Since the movement is diffusion in the cell membrane (so-called diffusion in solids), it depends on the thickness of the foam, the type of solvent, the type of inorganic material and its amount, etc. For example, in the case of a plate-like rigid foam having a thickness of about 5 Gmm, it is preferable that the time be about 2 to 2 G hours. The drying time is preferably about 4 to 20 hours. In general, if the drying time is too short, there will be insufficient displacement of the air and the rigid foam will contract to a reduced pressure during cooling. On the other hand, if the length is too long, on the contrary, the vinyl chloride / vinyl acetate copolymer deteriorates and discolors.

The method of applying hot air drying to the rigid foam is, for example, on a table that has a structure that allows hot air to easily contact the foam, such as a net or punching metal. For example, there is a method of placing a foam, contacting the foam on the table with hot air of a predetermined temperature to dry the foam, and the like. In the present invention, instead of contacting with hot air, the foam may be left in a thermostat at a predetermined temperature or in a thermostat, but in this case, the foam may be left inside. Since the solvent vapor is full, it is preferable to displace the internal air so that the concentration is lower than the lower limit of the explosion limit of the solvent vapor for safety. What W

(20) The air used for the hot air is not particularly limited, and it is preferable that the air be normal air in consideration of operability, cost, and the like. .

Hot air drying was applied to the rigid foam to ensure that the residual solvent in the foam did not adversely affect the quality of the foam, and that the solvent vapor and blowing agent gas in the rigid foam were sufficiently replaced with air. Then, the rigid foam is usually cooled to room temperature and cured. The cooling method is not particularly limited, and may be left standing at room temperature for cooling, or may be cooled by contacting the cold air with the hard foam.

The expansion ratio of the obtained inorganic-filled rigid foam may be any as long as it satisfies the combustion characteristics.However, in consideration of physical properties such as thermal conductivity and economics, etc. It is preferably 50 times or more. However, when the expansion ratio exceeds 200 times, it is difficult to obtain a normal foam, and even if a foam is obtained, it is difficult to obtain a mechanical foam. Since the physical properties such as strength are not sufficient, it is preferable that the ratio be 2 GQ or less.

The thus obtained rigid foam of the present invention has a flame-retardant 1 in the surface test specified in J1SA1332 “flame-retardant test method for building interior materials and construction methods”. Since it passes the class, it can be suitably used, for example, as insulation for building structures subject to fire prevention regulations.

In addition, the rigid foam of the present invention not only passes the surface test, but also passes the model box test in the quasi-noncombustible material certification test certified by the Ministry of Construction. Since it can satisfy nonflammable standards, it can be used for a wide range of applications.

Hereinafter, the present invention will be described in detail with reference to Examples. The present invention is not limited to only such embodiments. Examples 1-2 and Comparative Examples 1-4

The raw materials shown in Table 1 were 35 parts by weight of rock wool, 100 parts by weight of calcium carbonate, 0 parts by weight of aluminum hydroxide, and 40 parts by weight, based on parts by weight of vinyl chloride resin. Each component was measured in advance so that the total amount was 5 QG 0 g at a ratio of 350 parts by weight of toluene and 3 parts by weight of STM g.

[Margins below]

a

Raw material no-α Description

Resin A Emulsifier: Sodium dodecyl benzene sulphonate, maximum content of vinyl sulphate: 8.0 double dots, polymerization degree: 1850 L agent: Sodium dodecyl benzene sulphonate, content of vinyl acetate: 4.1% by weight, degree of polymerization: 2080 Resin c? L agent: sodium lauryl sulfate, vinyl acetate containing halo: 8.0% by weight, degree of polymerization: 1800

Resin D emulsifier: sodium lauryl sulfate, content of butyl sulfate: 3.9% by weight, polymerization degree: 2170

Vinyl chloride

Resin E emulsifier; sodium persulfate, vinyl acetate containing halo: 2.8 double halo, degree of polymerization: 1550

Resin

Resin F? L agent: sodium dodecylbenzenesulfonate, vinyl acetate content: 0 double halo%, degree of polymerization: 2400 resin G emulsifier: ο [-olefin sulfonate, halo containing tungstic acid bur: 8% by weight, polymerization degree: 1850

Resin H emulsifier: fatty acid, vinyl diester content: 8% by weight, degree of polymerization: 1850

Fat I emulsifier: sodium dodecylbenzenesulfonate, halo containing butyl acid 3.9% by weight, degree of polymerization: 2280

¾ ■ ¾] Diameter about 5 fi m, average fiber length 70-250 μm

Charcoal Carbonated Rushidum (particle size 150 mesh pass)

Nothing

Aluminum hydroxide Aluminum hydroxide (Average particle size 1-40 m)

Kaolin average diameter about 5 im, thickness about 2 jum, aspect ratio 3

AIBN Azobisui Soptitrol

Decomposition type foaming agent

AMBN 2,2'-azobis (2-methylbutyronitrile)

Organic solvent Toluene

Stabilizer STMg Magnesium stearate

(Meta) query

TEGDM Triethylene glycol dimethacrylate (Molecular weight 286)

Lurate ester

Next, a raw material other than the foaming agent A 1 BN is put into a double-armed kneader with an effective capacity of 3 liters, and hot water is passed through the Niego jacket. The kneading temperature was adjusted so as to be 8 G to 1 Qΰ ° C, and the mixture was kneaded for 10 to 50 minutes to obtain a mixture.

Then, pass warm water through the Nieder jacket, lower the temperature of the mixture in the Nieter to about 80 ° C, and then inject AIBN. Subsequently, the mixture was kneaded for about 10 minutes to obtain a foamable composition.

The foamable composition is filled into an aluminum alloy mold having a carrier dimension of 16 Oram X 160 mm x 22 mm, the mold is covered with an aluminum plate, and hydraulically driven. The temperature was set from room temperature (about 2 fl ° C) to 110 in about 10 minutes after setting in a hot-press machine.

The tightening pressure of the hot press was about 150 kg per 1 cm ^{2 of} mold area in each example and each comparative example.

Next, mold 110-140. After holding at 10 ° C for 10 minutes, hot water is passed through the cooling plate of the hot press machine to lower the mold temperature to a temperature suitable for foaming (25-60 ° C) in about 20 minutes. Was.

After that, when the tightening pressure of the hot press was released, the mold contents instantaneously burst into bubbles.

Each of the obtained foams had a beautiful appearance, and the uniformity of bubbles on the cut surface was also good.

Place the foam in a hot air circulating oven and use resin AC or E at 50 ° C, respectively, or use resin B or D, respectively. 75 in the end. In C, each was left for about one day to remove and evaporate the toluene.

The physical properties of the obtained foam were measured for the foam density, foaming ratio, closed cell rate, water absorption, and the test according to the following methods. The results are shown in Table 2. (Ii) Apparent density

A cube having a side length of 2 Omm was cut out from the foam, and its volume and weight were measured to calculate the apparent density of the foam.

(Mouth) Expansion ratio ''

The apparent density of the vinyl chloride resin in the foam is calculated from the amount of the inorganic substance, the foaming agent, and the amount of the stabilizer (parts by weight) based on 100 parts by weight of the vinyl chloride resin.

[Apparent density of vinyl chloride resin in foam]

= [Apparent density of foam (/ m ³ )] X 100 / (100 +

[Amount of inorganic substance (parts by weight) + amount of blowing agent (parts by weight) + amount of stabilizer (parts by weight)]) (kg / m ³ ). One technique, the specific gravity of the vinyl chloride resin 1. 4 X 10 ³ and to the expansion ratio formula:

[Expansion ratio] = [1. X 10 ^{ΰ ΰ Apparent} density of vinyl chloride resin in foam] (times)

It was calculated from

(C) Closed cell rate

Based on ASTM D-56, measurements were made using an air-comparison hydrometer manufactured by Toshiba Beckman Co., Ltd.

(2) Water absorption

JI δ A 9511 Measured according to the method specified in “Polystyrene foam insulation”.

(E) Surface test

(i) Temperature time area

It was measured according to the surface test specified in JIS A 1321 “Test method for flame retardancy of building interior materials and construction methods”.

(i U combustion shrinkage

The dimensions before and after the test of the sample whose temperature and time area were measured Measure and formula:

[Burning shrinkage]

= (1-[dimension after test] / [dimension before test]) X 100

It was calculated more.

(i i i) crack

Evaluation was made by visual observation.

Example 3

Except that the amount of AIBN used in Example 2 was changed from 40 parts by weight to 30 parts by weight, a foam was made in the same manner as in Example 2, and then a hot press machine was used. After removal from the foam, the foam was further brought into direct contact with steam at a steam temperature of 65 to 80 ° C for 10 minutes, and then the temperature was increased to 7 (! To Π) to remove and evaporate the solvent. A foam was obtained in the same manner as in Example 2 except that the foam was left on a flat wire mesh in a hot air circulation type oven adjusted to G ° C for 20 hours. The physical properties of the foam thus obtained were examined in the same manner as in Example 1. The results are shown in Table 2.

[Margins below]

Table 2 Physical properties of hard foam

Example vinyl chloride

Surface test

No. resin Apparent density Expansion ratio Closed cell ratio Water absorption

(kg / m3) (times) (° / o) (g / 100cm ² ) Temperature time area Combustion shrinkage

Kurano, Rino (° c · minute) (° / ο)

1 Resin A 86 100 95 0.02 0 1.4 None

2 Resin B 82 105 97 0.03 0 0.9 None

3 Resin B 81 106 91 0.04 0 0.9 None Comparative example 1 Resin C 82 105 7 0.21 0 0.5 Penetration

2 Resin D 86 100 94 0.03 0 1.5 Penetration

3 Resin E 333 26 53 0.14 0 0.6 Through

4 Resin F

According to the results shown in Table 2, the foams of Comparative Examples 1 and 2 in which foams were prepared from vinyl chloride-vinyl acetate copolymers with resins similar to those in Examples 1 and 2 were used. The body has satisfactory values in terms of expansion ratio, closed cell rate, and water absorption, respectively. However, sodium lauryl sulfate (SLS) is used as an emulsifier. Since cracks were used, cracks occurred during combustion during the surface test.

In Comparative Example 3, the content of vinyl acetate was small, so that the closed cell ratio was reduced, the foaming ratio was low, and the SLS was further reduced. As a result of the polymerization, cracks were generated during combustion in the surface test.

In Comparative Example 4, since the resin F was a vinyl chloride homopolymer, the resin F was scattered at the time of foaming, and the foam was not obtained.

Examples 4 to 9 and Comparative Examples 5 to 6

A hard foam was obtained in the same manner as in Example 1 except that the composition of the foamable composition was changed as shown in Table 3 in Example 1.

The physical properties of the obtained rigid foam were examined in the same manner as in Example 1. The results are shown in Table 4.

[Margins below]

Three

Composition of foaming composition (parts by weight)

Example Example

No.PVC decomposition type

* H m 3¾. Resin-based resin rock wool charcoal calcium hydroxide aluminum foaming agent

4 1 A UU oo 1 ηπ U Λ R \ I AC P JV-i-, ou I lvlg O

5 im Π i l Aoo 25 1 10 370 AIBN 40 Tornolen 350 STMg 3

6 Resin I 100 65 300 AIBN 40 Tornolen 350 STMg 3

7 Resin I 100 30 170 370 AIBN 40 Tornolen 450 STMg 3

8 Resin I 100 35 370 270 AIBN 40 Tornolen 400 STMg 3

9 Resin I 100 35 100 270 AIBN 40 Tornolen 350 STMg 3 Comparative example

5 Resin G 100 35 100 370 AIBN 40 Tornolen 350 STMg 3

6 Resin H 100 5 100 370 AIBN 40 Tornolen 350 STMg 3

4 flS ¾ ½t-page

Example surface test

Number Apparent density Expansion ratio Closed cell ratio Water absorption

(kg / m3) (times) (%) (g / 100cm2) Temperature time area Combustion shrinkage

| \ No, crack (c · minute) (%)

4 83 104 92 0.04 0 0.9 None

5 80 108 98 0.02 0 0.4 None

6 62 106 92 0.08 0 0.9 None

7 105 104 90 0.07 0 0.5 None

8 97 103 91 0.05 0 0.2 None

9 83 104 92 0.06 0 0.5 None Comparative example

5 82 105 87 0.04 0 1.7 messages

6 83 104 92 0.04 0 1.9 messages

From the results shown in Table 4, all of the samples obtained in Examples 4 to 9 have no cracks, have a high closed cell rate, and have a small combustion shrinkage rate. I understand.

Example 1 (! ~ U and Comparative Examples 7 ~ 8

A hard foam was obtained in the same manner as in Example 3, except that the composition of the foamable composition was changed as shown in Table 5.

The physical properties of the obtained rigid foam were examined in the same manner as in Example 1. Table 6 shows the results.

[Less margin]

Five

Π M M)

Example

PVC (Metal) Number Decomposition type

Organic solvent Stabilizer Acrylic acid-based resin Rock wool Charcoal Aluminum hydroxide Kaolin Blowing agent Ester

1 0 Resin I 100 35 100 370 AIBN 30 Tornolen 350 STNg 3

1 1 Resin I 100 35 370 100 AIBN 30 Tozoreen 350 STMg 3 5

1 2 Resin I 100 35 270 AIBN 30 Tornolen 250 STMg 3 Comparative example

7 Resin F 100 35 100 370 AIBN 30 Tonolen 350 STMg 3

8 Resin I 100 0 135 370 AIBN 30 Tornolen 350 STMg 3

Table 6 Physical properties of hard foam

Example surface test

Number Apparent density Expansion ratio Closed cell ratio Water absorption

(kg / m3) (times) (%) (g / 100cmZ) Temperature time area Combustion shrinkage

Crack (.c · minute) ()

10 78 111 96 0.03 0 1 None

Π 80 108 93 0.06 0 0,4 None

12 69 104 90 0.09 0 1.5 None

7

8 77 112 97 0.02 0 Collapse

According to the results shown in Table 6, the hard foams obtained in Examples 10 to 12 had no cracks and had excellent combustion characteristics. I understand.

In Comparative Example 7, the foam was not contained in the foam because the resin did not improve up to the level of the foam because it did not contain vinyl acid acid. In Comparative Example 8, since rock wool was not present in the foam, it was difficult to maintain the shape of the burning surface in the surface test. Then, it broke down. Examples U to 33

In Example 3, the materials shown in Table 1 were used as the raw materials of the foamable composition, and the composition of the foamable composition was changed as shown in Table 7. In the same manner as in Example 3, a hard foam was obtained.

As physical properties of the obtained rigid foam, the sparkling density, the expansion ratio, and the closed cell ratio were set in the same manner as in Example 1, and the rectangular ratio and the flatness were determined by the following methods. The measurement was performed according to the following. Table 8 shows the results.

(Rectangle rate)

It can be determined by dividing the shortest width of the obtained rigid foam in the plane direction by the longest width.

(Flat rate)

It can be obtained by dividing the minimum thickness in the thickness direction of the obtained rigid foam by the maximum thickness.

[Margins below] Table 7 Composition of foaming composition (heavy sound

Machine

Example Vinyl chloride Scale-like inorganic substance

¾ Organic solvent defined Coal power 7Κ

tn-based resin Blowing agent (meth) Acrylic acid ester (molecular weight)

Iwate ass

J use

蒱頹 Aluminum

Kuki Hiki

13 Resin I 100 AIBN 30 Tornolen 350 I iylg OO My power 130 20 180 270 Triethylene glycol dimethacrylate (286) 5

14 Resin I 100 AIBN 30 Tonoren 350 c

1 lyig q

My power 130 50 150 270 Ethylene glycol dimethacrylate (286) 5

15 Resin I 100 AIBN 30 Tonore 350 x syig oO My power 130 100 100 270 h Ethylene glycol dimethacrylate ( ₂₈₆ ) 5

16 Resin I too AIBN 30 Tonoren 350 CTAAn-Q

OO talc 20 100 100 270 Triethylene glycol dimethacrylate (286) 5

17 Resin I 100 AIBN 30 Tonolen 350 Orr

O l g O O Kaolin 10 100 100 270 Triethylene glycol dimethacrylate (286) 5

18 Resin I L00 AIBN 30 Tosoleen 350 1 x iS OO Kaolin 3 20 180 270 Triethylene glycol dimethacrylate (286) 5

19 Resin I 100 AfflN 30 Tonolen 350 OO Kaolin 3 50 150 270 Triethylene glycol dimethacrylate (286) 5

20 Resin I 100 AIBN 30 Triene 350 O Kaolin 3 100 100 270 Triethylene glycol dimethacrylate (286) 5

21 Resin I 100 AIBN 30 Trinoleen 350 STMg 3 35 Rin 3 100 100 270 Triethylene glycol dimethacrylate (286) 2

22 Resin I 100 AIBN 30 Toluene 350 STMg 3 35 Kaolin 3 100 100 270 Triethylene glycol dimethacrylate (286)

23 Resin I 100 AIBN 30 Toluene 350 STMg 3 35 Rare 3 100 100 270 Triethylene glycol dimethacrylate (286) 20

24 Resin I 100 AIBN 30 Toluene 350 STMg 3 35 Kaolin 3 100 100 270 1, 3-Butylene glycol dimethacrylate (226) 5

25 Resin I] 100 AIBN 30 Toluene 350 STMg 3 35 Kaolin 3 100 100 270 1,9-Nonanediol dimethacrylate (282) 5

26 Resin I] 100 AIBN 30 Train 350 STMg 3 35 Kaolin 3 100 100 270 Trimethylolpropane trimethacrylate ( ₃₃₈ ) 5

27 Resin I] [00 AIBN 30 Toluene 350 STMg 3 35 Kaolin 3 100 100 270 Polyethylene glycol diacrylate (308) 5

28 Resin I 1 100 AIBN 30 Toluene 350 STMg 3 35 Kaolin 3 100 100 270 1,6--Hexanediol diacrylate (220) 5

29 Resin I 1 100 AIBN 30 Tonoren 350 STMg 3 35 Kalin 3 100 100 270 Trimethylolpropane triatrate (296) 5

30 Resin I] 100 AD3N 30 Train 350 STMg 3 35 200 270

31 Resin I 1 100 AIBN 30 Tonolen 350 STMg 3 35 200 270 Total V Ethylene glycol dimethacrylate (286) 5

32 Resin I 1 ίΟΟ AIBN 30 Toluene 350 STMg 3 35 Kaolin 1 100 100 270 · · Ethylene glycol dimethyl acrylate (286) 5

33 Resin I 1 ίΟΟ AIBN 30 Toluene 350 STMg 3 35 My strength 130 10 190 270 Triethylene glycol dimethacrylate (286) 5

Physical properties of hard foam

Example

No.Capacity Density Expansion ratio Closed cell ratio Rectangular ratio Uneven ⁵ P ratio

V «- & / ^lu Roh ια Roh, / 0 Roh f one Bruno

13 86 100 95 0.728 0.917

14 88 98 82 0.786 0.923

15 91 95 90 0.853 0.930

16 88 98 94 0.720 0.869

17 78 110 93 0.812 0.914

18 77 112 98 0.705 0.905

19 82 105 96 0.725 0.908

20 53 117 93 0.742 0.917

21 91 95 90 0.8ο6 0.953

22 78 110 98 0.822 0.917

23 73 118 99 0.711 0.902

24 83 104 92 0.713 0.915

25 79 109 96 0.727 0.922

26 85 102 94 0.746 0.937

27 94 92 91 0.865 0.977

28 88 98 92 0.718 0.989

29 94 92 90 0.873 0.969

30 82 105 93 0.642 0.822

31 77 112 98 0.615 0.798

32 81 107 97 0.681 0.711

33 80 108 93 0.672 0.868

As is clear from comparison between Example 13 and Example Π shown in Table 8, a part of calcium carbonate has a specific aspect ratio. It can be seen that the rectangularity and the flattening rate can be improved by substituting the inorganic substances.

In addition, as is apparent from comparison between Example 18 and Example, it is clear that (Metal) acrylate must be blended (Example 35), Although cavities are seen, when (meta) concrete is combined (Example U), it can be seen that a rigid foam without cavities is obtained. I do. Industrial applicability

According to the production method of the present invention, it is possible to industrially and easily produce an inorganic-filled foam having a high closed cell rate and a high expansion ratio, having excellent combustion characteristics. . Further, according to the production method of the present invention, it is possible to produce an inorganic-filled foam having a good rectangular ratio.

In addition, the rigid foam of the present invention passes the first grade of flame retardancy in the surface test prescribed in “flame retardancy test method for interior materials and construction methods of buildings” in ISA 1321. Therefore, it can be suitably used, for example, as heat insulating material for building structures subject to fire regulations.

Claims

The scope of the claims

1. (A) Chlorinated by polymerization using alkylbenzensulfonate as an emulsifier and having a vinyl acetate content of 3 to 2 Q% by weight. (B) Inorganic substance containing inorganic particulate matter and inorganic fiber having a diameter of 1 μιη or more, (C) water-insoluble solvent, and (D) An inorganic-filled rigid foam obtained by foaming a foamable composition comprising a decomposable foaming agent.

2. The rigid foam according to claim 1, wherein the average polymerization degree of the vinyl chloride-vinyl acetate copolymer is 150 (! To 5,000).

3.】 1 SA 21 Hardness according to claim 1 or 2, which passes the flame retardant class 1 in the surface test specified in “flame retardancy test method for building interior materials and construction methods” Foam.

4. The rigid foam according to any one of claims 1, 2 and 3, which is sodium dodecylbenzensulfonate emulsifier.

5. The rigid foam according to any one of claims 1, 2, 3 and 4, wherein the inorganic particles are scaly inorganic particles having an aspect ratio of 2 or more.

6. The rigid foam according to claim 5, wherein the scaly inorganic particulate matter is at least one selected from kaolin, cray, talc, and my strength.

7. Claims in which the foamable composition contains a (meth) acrylic ester having two or more (meth) acrylic ester groups. Item 7. A rigid foam according to item 5 or 6.

8. The rigid foam according to any one of claims 1, 2, 3, 4, 5, 6, and 7, wherein the inorganic fiber is rock wool.

9. The amount of inorganic substances used is vinyl chloride-vinyl acetate copolymer The rigid foam according to any one of claims 1, 2, 3, 45, 6, 7 and 8, wherein the amount is 95 to 95 parts by weight based on 100 parts by weight.

10. The rigid foam according to claim 1, 2, 3, 3, 4, 5, 6, 7, 8, or 9 wherein the water-insoluble solvent is toluene or xylene.

Π. The amount of the water-insoluble solvent used is 1 to 7 parts by weight per 1 part by weight of the vinyl chloride-vinyl oxalate copolymer. Claims 1, 2, 3, 4, 5, 6, 7, A rigid foam as described in 8, 9 or 10.

12. Claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 wherein the decomposition type foaming agent generates nitrogen gas by thermal decomposition. Rigid foam.

13. The rigid foam according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 9, 1 U or 12 comprising a stabilizer.

14. (Α) A vinyl chloride-vinyl peroxy copolymer copolymer which has been polymerized using alkylbenzensulfonate as an emulsifier and has a vinyl nitrate content of 3 to 20% by weight. Coalesced, (Β) inorganic particulates and inorganics containing inorganic fibers with a diameter of 1 m or more, (C) water-insoluble solvent, and (D) foaming from decomposable foaming agent The composition is kneaded at a temperature not lower than the temperature at which the vinyl chloride-vinyl acetate copolymer and the water-insoluble solvent exhibit compatibility, and pressurized in a temperature range suitable for decomposition of the decomposable foaming agent. After that, it is cooled to a suitable temperature for foaming, foamed by depressurizing, and then evaporates the solvent by heating. .

15. The average polymerization degree of vinyl chloride- ^ acid vinyl copolymer

15. The method for producing a rigid foam according to claim 14, wherein the rigidity is 150 G to 5 flOG.

16. The emulsifier is sodium dodecylbenzensulfonate A method for producing a rigid foam according to claim 14 or 15.

V. The method for producing a rigid foam according to claim 14, 15, or 16, wherein the inorganic particulate material is a flaky inorganic particulate material having an aspect ratio of 2 or more.

18. The method for producing a rigid foam according to claim 5, wherein the scaly inorganic substance is at least one selected from kaolin, crepe, tanolek, and myo power.

19. Claims in which the foamable composition contains a (meth) acrylic acid ester having two or more (meth) acrylic acid ester groups. Item 18. The method for producing a rigid foam according to item 18 or 18.

20. The method for producing a rigid foam according to claim 14, 15, 16, 118 or 19, wherein the inorganic fiber is rock wool.

21. The amount of inorganic substances used is vinyl chloride-vinyl oxyacid copolymer

The method for producing a rigid foam according to claim 14, 15, 16, 17, 18, 19 or 20, which is 95 to 950 parts by weight based on 100 parts by weight.

22. The rigid foam according to claim 14, 15, 16, 17, 18, 19, 20, or が, wherein the water-insoluble solvent is toluene and / or xylene. Manufacturing method.

23. Claims 14, 15, 16, 17, 18 in which the amount of the water-insoluble solvent used is 100 to 100 parts by weight with respect to 100 parts by weight of vinyl chloride monovinyl copolymer. 23. The method for producing a rigid foam according to claim 19, 20, 20, 21 or 22.

24. Claim 14, 15, 16, 17, 18, 19, 20, 21, 21 wherein the decomposable blowing agent generates nitrogen gas by thermal decomposition.

Production of rigid foam as described in 22 or fi fi o

25. The method of producing a rigid foam according to claim 14, 15, 16, 17, 18, 19, 20, 21, 22, or which comprises a stabilizer.

26. (A) Vinyl chloride which has been polymerized using alkylbenzensulfonate as an emulsifier and has a vinyl sulphate content of 3 to 20% by weight. (B) inorganic particulates and inorganic materials containing inorganic fibers having a diameter of 1 m or more, (C) water-insoluble solvents, and (D) decomposable foaming agents The foamable composition is kneaded at a temperature or higher at which the vinyl chloride-vinyl acetate copolymer and the water-insoluble solvent exhibit compatibility, and is added in a temperature range suitable for the decomposition of the decomposable foaming agent. After pressurizing, the mixture is cooled to a suitable foaming temperature, depressurized and foamed, and the foam is brought into direct contact with steam to form foam, and then heated. Manufacturing of inorganic-filled rigid foams, which are characterized by the volatilization and removal of solvents.

27. The average degree of polymerization of vinyl chloride-vinyl acid copolymer

27. The method for producing a rigid foam according to claim 26, wherein the rigid foam is 1500) to 51) {) ().

28. The method for producing a rigid foam according to claim 26 or claim 7, wherein the emulsifier is sodium dodecylbenzensulfonate.

29. The method for producing a rigid foam according to claim 26, 27 or 28, wherein the inorganic particles are scaly inorganic particles having an aspect ratio of 2 or more.

30. The method for producing a rigid foam according to claim 29, wherein the scaly inorganic substance is at least one selected from kaolin, cray, talc, and mica.

31. The effervescent composition contains (meth) acrylic acid ester having two or more (meth) acrylic acid ester groups. Or a method for producing a rigid foam according to 30.

32. The method for producing a rigid foam according to claim 28, 29, 30, or 31, wherein the inorganic fiber is rock wool.

33. Claims 25, 26, Π, 28.29, 30.31 wherein the amount of the inorganic substance used is 95 to 950 parts by weight with respect to 100 parts by weight of vinyl chloride-vinyl acetate copolymer. Is a method for producing a rigid foam according to 32.

34. The method for producing a rigid foam according to claim 27, 28, 29, 30, 31, 32 or Π, which is a water-insoluble solvent-powered toluene and / or xylene. .

35. Claims 26, 27, 28, 29, 30. 31 The amount of water-insoluble solvent used is 100 to 700 parts by weight per 1 QQ parts by weight of vinyl chloride-vinyl acetate copolymer. 35. The method for producing a rigid foam according to claim 32, 33, or 34.

36. The method according to claim 26, 27, 28, 29, 33, 31, 32, 33, 34, or 35, wherein the decomposable blowing agent generates nitrogen gas by thermal decomposition. Manufacturing method of rigid foam.

37. The method for producing a rigid foam according to claim 26, Π, 28, 29, 30, 31, Π, Π, or 34 or 35, which comprises a stabilizer.