JP2018109137A - Thermal expansion vinyl chloride resin material and thermal expansion vinyl chloride resin material production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermal expansion vinyl chloride resin material that may effectively exhibit a function of blocking flame and smoke even in a low temperature region, can be expanded to be an expanded body with high caking power and excellent shape retention and mechanical strength, and can impart water resistance to a product thereof, and a thermal expansion sheet using the same.SOLUTION: A thermal expansion vinyl chloride resin material contains a vinyl chloride resin, a plasticizer for the resin, a thermal expansion graphite, a dehydrochlorination catalyst for the vinyl chloride resin, and a dehydrochlorination inhibiting compound. The dehydrochlorination inhibiting compound is a compound with an amino group and/or ammonium group which has a function of inhibiting a catalytic function of the dehydrochlorination catalyst at temperature of 160-240°C in the beginning of heating. The caking power of an expanded body obtained by heating at 800°C is 0.8 kgf or more.SELECTED DRAWING: None

Description

  The present invention relates to a thermally expandable vinyl chloride resin material and a method for producing a thermally expandable vinyl chloride resin material. In particular, an expanded body that can effectively exhibit a flame and smoke blocking function in a low-temperature region, and is heated and expanded, has excellent shape retention and mechanical strength, and according to a preferred embodiment, a product such as a thermally expandable sheet The present invention relates to a heat-expandable vinyl chloride resin material and a method for producing a heat-expandable vinyl chloride resin material. The present invention suppresses elution of components due to rainwater or the like when a product in which the form of the thermally expandable vinyl chloride resin material is a thermally expandable sheet, putty or paint is exposed to an outdoor environment, for example. The present invention relates to a technique for providing a heat-expandable vinyl chloride resin material that can be made excellent in functionality.

  In the field of building materials, fire resistance performance is regarded as important, and various materials having fire resistance performance have been developed. Expandable graphite has the property that its volume expands rapidly upon heating. Utilizing this property, expandable graphite is incorporated into a resin in the form of a sheet (hereinafter also referred to as a thermally expandable sheet) or an indeterminate shape. (Putty, paint, coating) are manufactured and placed in a space, and used as a fire spread prevention material that causes expansion by heat and slows down the fire around a fire. In this case, the resin component used in combination with expansive graphite not only realizes high incombustibility and flame retardancy of the resin material itself as fire resistance, but also forms an effective heat insulating layer in the event of a fire, and thereby flame and It must be capable of exhibiting smoke blocking function.

  As a resin component having such a function, there is a polyvinyl chloride resin. For example, Patent Document 1 discloses a thermally expandable vinyl chloride resin using flame retardancy and moldability of a polyvinyl chloride resin. Materials have been proposed. According to this resin material, it is said that continuous production by extrusion molding or the like is easy while maintaining good expandability and shape retention after expansion, and the structure obtained by expanding the molded body is: It is said that it has the same fire resistance as conventional and has the mechanical strength necessary to block fire and smoke.

  In order to improve flame retardancy, not only the above-mentioned thermally expandable vinyl chloride resin materials, flame retardants are used in thermally expandable resin materials. In the field used as a fire spread prevention material that slows down the surroundings of the fire, polyphosphoric acid flame retardants are frequently used in terms of their flame retardant effect and cost.

  The present inventors have already been able to effectively exert a flame and smoke blocking function particularly in a low temperature range, and a thermally expandable vinyl chloride system in which the expanded body after expansion has excellent shape retention and mechanical strength. We are proposing resin materials. The feature of this technology is that it has newly found a dehydrochlorination catalyst having a function of promoting dehydrochlorination of vinyl chloride resin at the expansion start temperature of expansive graphite. This makes it possible to provide a product excellent in shape retention and mechanical strength, which has a high caking force of 0.8 kgf, which is obtained by heating at 800 ° C., which has not been realized with an expandable resin material. And also in this proposal, the polyphosphoric acid type flame retardant often used by the prior art is used as a flame retardant.

Japanese Patent No. 4250153 Japanese Patent No. 5992589

  In the process of further studying the above-described conventional technology already proposed, the present inventors can obtain the thermally expandable vinyl chloride resin material provided by the above-described technology by heating to 800 ° C. Although the caking force of the expanded body is as high as 0.8 kgf, it is possible to realize a product excellent in shape retention and mechanical strength and excellent in fire resistance, but the resin material has a problem to be examined in terms of water resistance, He recognized that there was a need to improve water resistance. That is, for example, the sheet-like thermally expandable vinyl chloride resin material provided by the above-described conventional technology is exposed at the boundary between the interior and exterior of a window frame or doorway door that is exposed to rainwater facing the exterior. When applied as a flame retardant, the water resistance is inferior, and the components of the thermally expandable vinyl chloride resin material are eluted by rainwater, etc., which causes appearance defects due to the precipitation of the eluate. I found out that Depending on the degree of defects in appearance, due to this, the performance of the expansion body obtained by heating and expanding products such as thermal expansion sheets used as fire spread prevention materials in the event of a fire is reduced. However, there is a concern that a situation may occur in which the high performance inherent to the expandable body is not effectively exhibited. Therefore, improvement of water resistance in a product made of a heat-expandable vinyl chloride resin material is a very important problem. At the same time, it is possible to stably provide a higher-quality product that has improved the caking force of the expandable body obtained by heating, improved the fire resistance with better shape retention and mechanical strength, and more. It was recognized that technological development is desired, and that further improvement is necessary for that purpose.

  Therefore, the object of the present invention is to effectively exert a flame and smoke blocking function even in a low temperature range, and the expanded body after expansion heated to 800 ° C. exhibits a higher cohesive force, In a variety of environments where the product is of high quality with excellent mechanical strength, and the product can be used facing the outside and has excellent water resistance even when exposed to rainwater, etc. To stably provide products such as a heat-expandable vinyl chloride resin material of higher quality and a heat-expandable vinyl chloride resin material that can be applied in the field of view, and that has a better flame and smoke barrier function. is there.

  The above object is achieved by the present invention described below. That is, the present invention provides a vinyl chloride resin, a plasticizer for the resin, thermally expandable graphite having an expansion start temperature of 180 to 240 ° C., a dehydrochlorination catalyst for the vinyl chloride resin, and dehydrochlorination suppression. A heat-expandable vinyl chloride resin material comprising a compound, wherein the heat-expandable graphite is contained in an amount of 50 to 150 parts by mass in 100 parts by mass of the vinyl chloride resin, and the dehydrochlorination catalyst has an average polymerization Sample with a composition comprising 52 parts by mass of a vinyl chloride resin having a degree of 400 to 3000, 42.8 parts by mass of dioctyl phthalate as a plasticizer for the resin, and 5.2 parts by mass of a dehydrochlorination catalyst When A is heated at 180 ° C. for 15 minutes and then at 190 ° C. for 15 minutes, the weight loss of the sample A is 25% by mass or more, and the vinyl chloride resin 100 of the dehydrochlorination catalyst The amount added to parts by mass is average 52 parts by mass of a vinyl chloride resin having a degree of synthesis of 400 to 3000, 42.8 parts by mass of dioctyl phthalate as a plasticizer for the resin, and 100 parts by mass of a vinyl chloride resin having an average degree of polymerization of 400 to 3000 For sample B to which a desired amount of dehydrochlorination catalyst was added to the part, after heating at 180 ° C. for 15 minutes and then at 190 ° C. for 15 minutes, the weight loss of sample B was 25% by mass or more. The dehydrochlorination inhibiting compound is a compound having an amino group and / or an ammonium group having a function of inhibiting the catalytic function of the dehydrochlorination catalyst at a heated initial temperature of 160 to 240 ° C., 800 Provided is a thermally expandable vinyl chloride resin material characterized in that an expanding body obtained by heating at 0 ° C. has a caking force of 0.8 kgf or more.

Preferred forms of the thermally expandable vinyl chloride resin material of the present invention include the following. The dehydrochlorination inhibitor is melamine polyphosphate, melamine polyphosphate, melam, melem, melamine phosphate, melamine polyphosphate metal salt, piperazine phosphate, ethylenediamine phosphate, melamine sulfate, melamine, melam, melem, melamine cyanurate Benzoguanamine, silane-coated ammonium polyphosphate, melamine-coated ammonium polyphosphate, urea and ammonium chloride; the dehydrochlorination inhibiting compound is melamine polyphosphate, melamine polyphosphate, melam, melem , Melamine cyanurate, melamine sulfate, melamine, benzoguanamine and silane-coated ammonium polyphosphate; The dehydrochlorination catalyst is made of metal zinc, zinc oxide, zinc carbonate, zinc chloride, copper, copper oxide, and iron chloride; The amount of elution when immersed in hot water at 95 ° C. for 24 hours is 2.5% or less on a mass basis; the thickness formed by the resin material is 1.5 to A test piece obtained by laminating a laminate of 1.6 mm and an area of 20 × 20 mm on a polyester nonwoven fabric having a density of 300 g / m ² is heated at 800 ° C., and the expanding body has a caking force of 1.0 kgf or more. The shape is a sheet and the thickness is 0.5 mm to 2.0 mm; the shape is a paste or paint; for installation on a window frame or door frame It is mentioned that .

  Another embodiment of the present invention is a method for producing a thermally expandable vinyl chloride resin material, wherein the expansion start temperature is 180 to 240 ° C. with respect to 100 parts by mass of the vinyl chloride resin. Using graphite in the range of 50 to 150 parts by mass, and further, a dehydrochlorination catalyst for promoting dehydrochlorination of the vinyl chloride resin at the expansion start temperature, and a dehydrochlorination inhibiting compound for inhibiting dehydrochlorination, In the production of a thermally expandable vinyl chloride resin material containing these using a vinyl chloride resin plasticizer, the dehydrochlorination catalyst is used as a vinyl chloride having an average degree of polymerization of 400 to 3000. Sample A was formulated by adding 52 parts by weight of a resin, 42.8 parts by weight of dioctyl phthalate as a plasticizer for the resin, and 5.2 parts by weight of a dehydrochlorination catalyst at 180 ° C. for 15 minutes. And then 15 at 190 ° C. When heated, the sample A is selected from substances whose weight loss is 25% by mass or more, and the amount of the dehydrochlorination catalyst added to 100 parts by mass of the vinyl chloride resin is determined by the average degree of polymerization. To 52 parts by mass of a 400-3000 vinyl chloride resin, 42.8 parts by mass of dioctyl phthalate as a plasticizer for the resin, and to 100 parts by mass of a vinyl chloride resin having an average polymerization degree of 400-3000. On the other hand, with respect to Sample B to which a desired amount of dehydrochlorination catalyst was added, after heating at 180 ° C. for 15 minutes and then at 190 ° C. for 15 minutes, the weight loss of Sample B would be within a range of 25% by mass or more. Furthermore, the dehydrochlorination inhibitor has an amino group and / or an ammonium group having a function of inhibiting the catalytic function of the dehydrochlorination catalyst at a heated initial temperature of 160 to 240 ° C. as the dehydrochlorination inhibitor compound. To provide a method for producing a thermally expandable vinyl chloride resin material, characterized in using a compound.

  As a preferable embodiment of the method for producing the thermally expandable vinyl chloride resin material of the present invention, the compound having an amino group and / or an ammonium group may be melamine polyphosphate, melamine polyphosphate melam melem, melamine phosphate, melamine Selected from the group consisting of polyphosphate metal salt, piperazine phosphate, ethylenediamine phosphate, melamine sulfate, melamine, melam, melem, melamine cyanurate, benzoguanamine, silane-coated ammonium polyphosphate, melamine-coated ammonium polyphosphate, urea and ammonium chloride Or at least one of the above.

  According to the present invention, an expanded body obtained by heating at 800 ° C. and expanding (hereinafter also referred to as “heated expanded body”) exhibits a higher caking force and is more excellent in shape retention and mechanical strength. In addition, a thermally expandable vinyl chloride resin material capable of more effectively exerting a flame and smoke blocking function from a low temperature range is provided. Moreover, according to the preferred embodiment of the present invention, the formed product such as a heat-expandable sheet is used, for example, facing the outdoors, and is excellent in water resistance even when exposed to rainwater, etc. There is provided a thermally expandable vinyl chloride resin material that is superior in flame and smoke barrier performance when used in an environment. The excellent thermally expandable vinyl chloride resin material provided by the present invention is not limited to a sheet shape, for example, a putty that can be used by filling an open space by using a paste, or a paint shape, By applying it to metal or wooden pillars and walls, or by applying it to electric wires, etc., it shows a higher caking force after expansion, and it is a useful heated expansion body that is superior in shape retention and mechanical strength. Thus, it is possible to provide various useful products that can form a thermally expandable coating or the like.

It is the figure which showed the relationship between heating time and a weight loss when the thermally expansible sheet of the Example of this invention and the thermally expansible sheet of a comparative example are heated to 160 degreeC. It is the figure which showed the relationship between the heating time and weight loss at the time of heating the thermally expansible sheet of the Example of this invention, and the thermally expansible sheet of a comparative example to 190 degreeC. It is the figure which showed the relationship between heating time and a weight loss when the thermally expansible sheet of the Example of this invention and the thermally expansible sheet of a comparative example are heated at 220 degreeC. It is the figure which showed the relationship between heating time and weight loss when the thermally expansible sheet of the Example of this invention and the thermally expansible sheet of a comparative example are heated to 240 degreeC. It is the figure which showed the test result which shows the foaming ratio at the time of heating at 200 to 800 degreeC.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments of the present invention. The present inventors have already proposed, based on a vinyl chloride resin, thermal expansion obtained by blending a plasticizer for the resin, thermally expandable graphite, and ammonium polyphosphate as a flame retardant. In the process of further studying the functional vinyl chloride resin material, the following solutions were obtained as a result of studying the use of products made of the resin material on window frames, etc., assuming various actual usage environments. I found a problem to be done. That is, the heat-expandable sheet formed of a conventional resin material may be thinned by rainwater or the like in an outdoor environment, and the sheet or covering may be thinned. It was found that further study is necessary in terms of stably supplying high-quality products. The problem of water resistance of a product used as a fire spread prevention material is important, and it has been recognized that there is an urgent need to improve this point in order to stably provide a higher quality product.

  First, as a result of intensive investigations on the inferior water resistance of a product made of the resin material (hereinafter simply referred to as “product”) in the conventional thermally expandable vinyl chloride resin material, It has been found that the component causing the poor water resistance is ammonium polyphosphate used as a flame retardant in the resin material. Ammonium polyphosphate does not hydrolyze even when dissolved in water, exists in a molecular state, has a very high stability, and is widely used as a flame retardant. When used as a flame retardant, the higher the degree of polymerization of ammonium polyphosphate, the higher the flame retardant effect. The degree of polymerization of commercial products is 100 to 500, and in some cases, the degree of polymerization exceeds 1000. On the other hand, it is said that the higher the degree of polymerization, the lower the solubility, and when the degree of polymerization exceeds 20, it is said that the solubility is drastically reduced. In the case of addition as a flame retardant, it is generally considered that there is no problem with water resistance.

  However, in the process of examining the composition of the resin material that will be a heating expansion body showing a higher cohesive force, the present inventors have made the previously proposed thermally expandable vinyl chloride resin material as a product In order to find that the cause is the ammonium polyphosphate used as a flame retardant and to provide a stable and high-quality product, this point should be considered. I understood it.

  Specifically, the present inventors blend a plasticizer for the resin, a thermally expandable graphite, a dehydrochlorination catalyst, and ammonium polyphosphate as a flame retardant based on a vinyl chloride resin. A product made of a heat-expandable vinyl chloride resin material was applied to window frames, etc., and various actual usage environments were considered. As a result, when placed in a harsh environment exposed to rainwater, etc., the appearance of sheets and coverings may change. In that case, there is a risk of hindering the fire spread prevention function. In any case, it has been found that in order to stably supply a high-quality product, it is necessary to further study the thermally expandable vinyl chloride resin material. That is, the present invention provides that the heated expanded body is excellent in shape retention and mechanical strength exhibiting higher caking force, and the product is also compatible with water resistance in harsh environments. It was made in consideration of the importance of developing a heat-expandable vinyl chloride resin material that can be made into an environmentally friendly product.

  First, the present inventors have intensively studied that the water resistance of the product may be inferior in the conventional heat-expandable vinyl chloride resin material. As a result, the occurrence of the phenomenon in which the water resistance is inferior It was found that it was related to the type of flame retardant in the material, and recognized that it was necessary to examine the flame retardant used in detail in order to improve the quality of the product. In the course of studying various components used as flame retardants, among the components having the function as flame retardants, amino group-containing compounds and / or ammonium groups having amino groups are included in the structure. When the present inventors use an ammonium group-containing compound in combination with the dehydrochlorination catalyst proposed by the inventors in the technology previously disclosed, the product has a higher caking than the heating expansion body has hitherto achieved. It has been found that the range of the above-mentioned compounds that can be used to exhibit strength is applicable and that a product having excellent water resistance can be provided by selecting the compounds in consideration of water resistance. The present inventors consider the reason why the above effect is obtained as follows. Hereinafter, the background to the present invention will be described, and the remarkable effects obtained by the configuration of the present invention will be described.

  The inventors of the present invention have so far conducted a study from a viewpoint unprecedented in the development of a material in which a heat expansion body can exhibit a better fire spread prevention function. As a result, a vinyl chloride resin and the resin In the heat-expandable vinyl chloride resin material containing the plasticizer and heat-expandable graphite, it can effectively exert the function of blocking the flame and smoke in a low temperature range, and the heat expansion body is high. The present inventors have found the presence of a dehydrochlorination catalyst that exhibits a caking force and is excellent in shape retention and mechanical strength. Details of this technique are described in Patent Document 2 cited above. That is, as defined in the present invention, this dehydrochlorination catalyst comprises 52 parts by mass of vinyl chloride resin having an average degree of polymerization of 400 to 3000, and 42.8 parts by mass of dioctyl phthalate which is a plasticizer of the resin. When the sample A having a composition obtained by adding 5.2 parts by mass of a dehydrochlorination catalyst was heated at 180 ° C. for 15 minutes and then at 190 ° C. for 15 minutes, the weight loss of the sample A was 25% by mass or more, It is a substance that shows high weight loss at low temperatures. Typical examples of the dehydrochlorination catalyst include metal zinc, zinc oxide, zinc carbonate, zinc chloride, copper, copper oxide, and iron chloride. The sample A is for determining the effect of the dehydrochlorination catalyst and does not contain a flame retardant.

  By using these dehydrochlorination catalysts, the heat-expandable vinyl chloride resin material containing the catalyst causes a significant decrease in the weight of the vinyl chloride resin at a low temperature range of 170 to 240 ° C. Carbonization is promoted, and the final heated expanded body exhibits a high caking force and is excellent in shape retention and mechanical strength. However, in the proposal in Patent Document 2, detailed examination of the flame retardant to be used is not performed, and ammonium polyphosphate is used as in the conventional case.

  In contrast, the present inventors based on the knowledge that ammonium polyphosphate added as a flame retardant is the cause of poor water resistance of the product, in order to improve this point, a vinyl chloride resin as a base A test was performed by adding various flame retardants to a resin material composed of thermally expandable graphite and a dehydrochlorination catalyst having the above-described function (containing a plasticizer). As a result, when a dehydrochlorination catalyst having the above-described functions was used, it was surprisingly found that the cohesive strength of the heated expansion body was further improved by combining compounds having specific structural characteristics. In addition, there are many kinds of compounds having specific structural characteristics that are found by the present invention to obtain this surprising effect, and by selecting these kinds, in addition to the high cohesive strength of the heated expansion body, the product This makes it possible to construct a thermally expandable vinyl chloride resin material that can improve the water resistance of the resin. Therefore, the thermally expandable vinyl chloride resin material of the present invention has higher performance and is applicable to harsh environments. It is possible to provide a variety of products that are superior to the above.

  The present inventors consider the reason why the heat-expandable vinyl chloride resin material of the present invention can be made superior in that the heat-expandable body exhibits a higher cohesive force as follows. The vinyl chloride resin usually promotes dehydrochlorination at a high temperature of 240 ° C. to 800 ° C., and finally becomes a carbide through a hard cured state. On the other hand, regardless of the composition, the thermally expandable graphite expands according to the temperature when the expansion start temperature is reached. Here, when a dehydrochlorination catalyst that causes a significant weight reduction of the vinyl chloride resin in a low temperature range of 170 to 240 ° C. is used, the progress of curing of the vinyl chloride resin and the thermal expansion having an expansion start temperature of 180 to 240 ° C. Since the expansion of the conductive graphite occurs in the same temperature range, the graphite expands with the vinyl chloride resin and carbonizes with dehydrochlorination, and as a result, it becomes a heated expansion body with a large cohesive force. Conceivable.

  On the other hand, when the dehydrochlorination catalyst is not used, dehydrochlorination of the vinyl chloride resin becomes insufficient in the temperature range where the expansion of the thermally expandable graphite starts. Thus, when the expansion of the graphite is completed when the resin is in the softened state, it is considered that the caking force of the heated expansion body cannot be supported because there is no sufficient entanglement of the resin. This is because, in a conventional product that does not use a dehydrochlorination catalyst, the heated expanded body is clearly inferior in caking force compared to the case where a dehydrochlorination catalyst is used, This is supported by the fact that shape retention and mechanical strength cannot be made excellent.

  As described above, the present inventors have further studied the above prior art for the purpose of realizing a higher quality product. First, when the resin hardens quickly before the expansion of the thermally expandable graphite, it naturally exists as a solid residue, but the heated expanded body is not sufficiently covered with the resin carbide, It does not have high caking power. This means that the presence of a dehydrochlorination catalyst that effectively proceeds the dehydrochlorination of the vinyl chloride resin is absolutely necessary. Furthermore, in order to obtain a more optimal heating expansion body capable of effectively exhibiting a flame and smoke blocking function, the present inventors have conducted dehydrochlorination of a vinyl chloride resin promoted by a dehydrochlorination catalyst, It was considered important to properly adjust the progress state that eventually becomes a carbide through the cured state and the expansion speed of the thermally expandable graphite. More specifically, it is necessary to adjust the progress rate of the vinyl chloride resin dehydrochlorination to the final carbide, which is promoted by the dehydrochlorination catalyst, and the expansion speed of the thermally expandable graphite. I thought it was. On the other hand, dehydrochlorination of vinyl chloride resin is said to proceed as a zipper, so the above idea promotes a zipper-like progression at low temperatures up to the expansion start temperature range of thermally expandable graphite. In other words, it is necessary to suppress the function of the dehydrochlorination catalyst to be added, that is, to use a compound that suppresses the function.

  Therefore, the present inventors changed the flame retardant, which is considered to be a causative component of the inferior water resistance of the product that triggered the present invention, to a low temperature up to the expansion start temperature range of the thermally expandable graphite. In the state, it investigated paying attention to the behavior which suppresses the function of the dehydrochlorination catalyst used together. As described above, generally, a phosphorus-based flame retardant is frequently used as the flame retardant. Further, it is known that when a phosphorus flame retardant and a nitrogen flame retardant are used in combination, a very effective flame retardant effect can be obtained. Intomescent flame retardants, that is, the idea of forming a char foam layer on the burning surface, phosphorus flame retardants produce char and nitrogen flame retardants nitrogen gas. It is said that it produces a synergistic effect because it causes foaming of the carbonized layer.

  Based on the above, the present inventors conducted a study using a wide range of flame retardants composed of phosphorus and / or nitrogen-containing compounds in the presence of the dehydrochlorination catalyst defined in the present invention. As a result of the examination, it was found that the combined use of the phosphorus-based flame retardant and the nitrogen-based flame retardant is not an essential factor for increasing the cohesive strength of the heated expansion body. And it discovered that the caking force of the heating expansion body can be improved more by using together an amino group containing compound and / or an ammonium group containing compound instead of the intomescent effect, and came to this invention.

  Specifically, the thermally expandable vinyl chloride resin material of the present invention is a resin based on a vinyl chloride resin, a plasticizer for the resin, and a thermal expandability whose expansion start temperature is 180 to 240 ° C. The composition of graphite and the vinyl chloride resin specified in the present invention as a dehydrochlorination catalyst was further used in combination with an amino group-containing compound and / or an ammonium group-containing compound having a function of suppressing the catalytic function of the dehydrochlorination catalyst. It is characterized by that. With this configuration, the thermally expandable vinyl chloride resin material of the present invention uses a dehydrochlorination catalyst that promotes dehydrochlorination in the low temperature range of 180 to 240 ° C., which is the expansion start temperature of the thermally expandable graphite. However, the progress of dehydrochlorination of vinyl chloride resin can be suppressed. On the other hand, since dehydrochlorination can be effectively advanced at high temperatures, it is possible to provide a product with better performance. According to the heat-expandable vinyl chloride resin material of the present invention using the above-described combination of substances, it is possible to more effectively exert a flame and smoke blocking function even in a low temperature range, and the heating expansion body is higher. The effect that it becomes the thing excellent by the shape retainability and mechanical strength which show caking force is acquired. In addition, in the above-described combination of substances, a heat-expandable sheet made of a resin material obtained by selecting and using an amino group-containing compound and / or an ammonium group-containing compound that is hardly soluble in water as a dehydrochlorination inhibiting compound. A new effect is obtained that the product such as the above has excellent water resistance. Specifically, it is possible to realize a product excellent in water resistance with an elution amount of 2.5% or less on a mass basis when the product is immersed in hot water at 95 ° C. for 24 hours.

  An amino group-containing compound and / or an ammonium group-containing compound having a function of suppressing the catalytic function of a dehydrochlorination catalyst, which is a dehydrochlorination suppressing compound constituting the present invention (hereinafter sometimes referred to simply as a dehydrochlorination suppressing compound) The effect of the heated expanded body on the cohesive force will be described later in detail. The present inventors reacted with hydrochloric acid generated by dehydrochlorination promoted by the dehydrochlorination catalyst used together, and as a result, abruptly I think that the polyeneization was suppressed.

  In the present invention, as the dehydrochlorination catalyst defined in the present invention, a dehydrochlorination catalyst is appropriately selected based on the difference in the effect of the metal powder and metal compound on dehydrochlorination described in Patent Document 2, and the chlorination is performed. A combustion test is performed at a high temperature (800 ° C.) in a system in which a thermal expansion graphite having an expansion start temperature of 180 to 240 ° C. and a dehydrochlorination inhibitor compound are blended with a vinyl resin, and the heated expanded body after the combustion test The cohesive strength was measured, and the effect produced by the combined use of a dehydrochlorination inhibitor was examined.

  First, in the course of the examination, examination tests were performed for the case where ammonium polyphosphate used as a flame retardant was used and the case where it was not used with the technique described in Patent Document 2. As a result, surprisingly, even when a metal compound or the like showing the effect of the dehydrochlorination catalyst defined in the present invention is present, when the ammonium polyphosphate is not added, the cohesive strength of the heated expanded body is It turns out that it is not good. On the other hand, even when ammonium polyphosphate is present, the caking force of the heated expansion body is insufficient when no metal compound showing the effect of the dehydrochlorination catalyst is added. As a result, in order to make the cohesive strength of the heat expansion body good, it was clearly found that the coexistence of a metal compound showing an effect of a dehydrochlorination catalyst and ammonium polyphosphate is necessary.

  As a result of further studies, the present inventors have used a dehydrochlorination catalyst and not only ammonium polyphosphate but also an amino group-containing compound and / or an ammonium group-containing compound, and these components coexist during heating. Thus, the present inventors have found that it is important to configure such a configuration, and have reached the present invention. Specifically, as a result of the following examination, it was found that the contribution to the improvement of the cohesive strength of the heated expanded body due to the use of ammonium polyphosphate in the above test was due to the ammonium group in the structure. Based on the above, further studies were made to achieve the present invention.

  As a result of conducting tests using various flame retardants generally used as similar flame retardants in place of ammonium polyphosphate used as the flame retardant used in the examination tests described above, I understood. Tests using metal polyphosphate compounds are less effective, while tests using melamine-coated polyphosphate and melamine, melam, and melem are good as with ammonium polyphosphate. Showed the effect. Moreover, the melamine sulfate, benzoguanamine, and melamine cyanurate which do not contain phosphorus content showed the effect which may be sufficient. Furthermore, surprisingly, the inorganic salt ammonium chloride also showed good effects. On the other hand, methylol melamine containing no amino group, phosphazene, phosphate ester and amino group methylolated did not show good results in the effect of improving the cohesive strength. Details of these examination results will be described later.

  In order to elucidate the reason why the above phenomenon occurs, the present inventors added the above-mentioned various phosphorus-based flame retardants and nitrogen-based flame retardants in the presence of zinc oxide exhibiting a catalytic effect as a dehydrochlorination catalyst. The weight loss at each temperature of 160 ° C., 190 ° C., 220 ° C., and 240 ° C., which is the expansion start temperature range of the thermally expandable graphite, was measured. The results are shown in FIGS.

  As a result, when each compound of melamine-coated polyphosphoric acid, melamine-melam-melem polyphosphate, melamine sulfate, benzoguanamine, melamine cyanurate having an amino group that showed an effect of improving the cohesive strength in the heated expanded body is present As shown in FIGS. 1 to 4, the loss curve with time was gentle at any temperature. The result was the opposite of the dehydrochlorination weight loss value in the absence of ammonium polyphosphate described above. On the other hand, in the case of each compound of phosphazene, phosphate ester, and methylol melamine having an amino group that does not contain an amino group that does not have a great effect on the improvement of the caking force in the heated expanded body, a large weight loss is obtained at 160 ° C. and 190 ° C. A curve is shown. Note that most of the compounds showed simple weight loss curves at higher temperatures of 220 ° C and 240 ° C.

  As described above, dehydrochlorination of vinyl chloride resin is considered to have a strong zipper effect, and there are many documents as listed below. For example, “Sakura Yamada, PVC and polymer, 20, (12), (1980)”, “Matsuo Onozuka, polymer, 13, (8), (1964)” can be mentioned. It is said that dehydrochlorination is promoted by electrophilic compounds such as zinc chloride and tin chloride, and the produced hydrochloric acid further exhibits a catalytic action. In order to stop this zipper effect, various stabilizers are known. P. Simon et al. Reported on the dynamic considerations based on metal stearates and described the effects of Mg and Pb. The literature includes “P. Simon, etc., PVC and polymer, 31, (9), (1991)”, “P. Simon, etc., PVC and polymer, 31, (10), (1991)”, and the like. . Since the stabilizer reacts with dehydrochlorination, it is considered that the dehydrochlorination is necessarily suppressed while the added stabilizer reacts and is consumed. For example, there is a report when dibutyltin maleate is used as a stabilizer (see, for example, “Kagawa et al., Tosoh Research Report, 12, (1998)”).

  From the above examination results, in order to obtain a better heat-expandable vinyl chloride-based resin material in which the heat-expandable body has a higher cohesive strength, its structure is dehydrochlorination having a strong dehydrochlorination effect. By adding in addition to the presence of the catalyst, dehydrochlorination is suppressed in the temperature range where the thermally expandable graphite starts to expand, and at the temperature above this temperature range, the amount of weight loss is increased. It was found that the coexistence of an amino group-containing compound and / or an ammonium group-containing compound, which functions as a hydrochloric acid inhibiting compound, is essential.

  Furthermore, in order to make products such as thermal expansion sheets excellent in water resistance, among the amino group-containing compounds and / or ammonium group-containing compounds, the solubility in water is very low. This compound can be easily realized by selecting the compound. Below, the component which comprises this invention is demonstrated.

<Dehydrochlorination inhibiting compound (amino group-containing compound and ammonium group-containing compound)>
The thermally expandable vinyl chloride resin material of the present invention can form a thermally expandable sheet having a certain thickness by using a comma coat molding method. Moreover, the heat-expandable body formed by foaming (expanding) the obtained heat-expandable sheet with heat does not collapse more easily and does not blow off easily with the pressure of flame, and has excellent shape retention. . According to the study by the present inventors, these effects are clearly different from those in the case where other flame retardants are used, and there are advantages in terms of effects. According to the study by the present inventors, in the thermally expandable vinyl chloride resin material of the present invention, the superiority of the effect by using an amino group-containing compound and / or an ammonium group-containing compound as its constituent component is It has been confirmed that this was brought about by obtaining a useful synergistic effect in combination with a component that functions as a dehydrochlorination catalyst defined in the present invention. In other words, in the thermally expandable vinyl chloride resin material of the present invention, an amino group-containing compound or an ammonium group-containing compound is used not as a mere flame retardant, but as a dehydrochlorination suppressing compound for a dehydrochlorination catalyst used in combination.

  Specific examples of the dehydrochlorination inhibiting compound constituting the present invention include ammonium polyphosphate, melamine polyphosphate, melamine polymelamine melam melem, melamine phosphate, melamine polyphosphate metal salt, piperazine phosphate, ethylenediamine phosphate, Examples include melamine sulfate, melamine, melam, melem, melamine cyanurate, benzoguanamine, silane-coated ammonium polyphosphate, melamine-coated ammonium polyphosphate, urea, and ammonium chloride.

  Moreover, it is preferable that the addition amount of a dehydrochlorination inhibitor compound is 50-150 mass parts with respect to 100 mass parts of vinyl chloride resin, More preferably, it is 70-100 mass parts. If the addition amount is too small, the flame retardancy effect and the shape retention effect at the time of expansion do not appear, and if it is too large, the molding process of the resin material tends to be difficult and the expansion rate is lowered, which is not preferable.

<Dehydrochloric acid catalyst>
As described above, the dehydrochlorination catalyst constituting the present invention is described in detail in Patent Document 2 cited above. Specific examples include metal zinc, zinc oxide, zinc carbonate, zinc chloride, copper, copper oxide, iron chloride, and the like, and any of them can be suitably used. However, the present invention is not limited to these substances. When the sample A defined in the present invention is heated at 180 ° C. for 15 minutes and then at 190 ° C. for 15 minutes, the weight loss of the sample A becomes 25% by mass or more. Any of them can be used. On the other hand, if the blending ratio is small, the effect of improving flame retardancy cannot be expected, and if it is too large, the viscosity of the resin material becomes high and blending becomes difficult, which is not preferable. From these points, it is preferable to be 50 to 150 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. However, the present invention is not limited to this range, and the sample B specified in the present invention is within a range where the weight loss of the sample B becomes 25% by mass or more after heating at 180 ° C. for 15 minutes and then at 190 ° C. for 15 minutes. It may be determined as appropriate.

<Vinyl chloride resin>
The vinyl chloride resin constituting the thermally expandable vinyl chloride resin material of the present invention has (1) vinyl chloride homopolymer or (2) an unsaturated bond copolymerizable with vinyl chloride and vinyl chloride. A monomer copolymer and a vinyl chloride copolymer containing 50% by mass or more of vinyl chloride can be used.

  Examples of monomers having an unsaturated bond copolymerizable with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate; acrylic acid and methacrylic acid; acrylic acid esters such as methyl acrylate and ethyl acrylate; Examples thereof include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; olefins such as ethylene and propylene; acrylonitrile; aromatic vinyl such as styrene; vinylidene chloride and the like.

  The average degree of polymerization of the vinyl chloride resin used in the present invention is not particularly limited, but is preferably 400 to 3,000, and more preferably 1,000 to 2,000. If the average degree of polymerization is less than 400, the mechanical properties of the obtained molded product may be inferior. When the average polymerization degree exceeds 3,000, the melt viscosity of the vinyl chloride resin at the time of molding becomes high, and molding may be difficult. If the molding temperature is raised to lower the melt viscosity, the vinyl chloride resin will be decomposed, making it difficult to obtain a good molded product. Although the heat-expandable vinyl chloride resin material of the present invention depends on a molding method, it is preferable to use a material having a viscosity of 5000 to 20000 mPa · sec at 25 ° C. The vinyl chloride resin may be used alone or in combination of two or more.

<Plasticizer>
The thermally expandable vinyl chloride resin material of the present invention contains a plasticizer for the resin. Examples of the plasticizer include bis (2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate, ditridecyl phthalate, phthalic acid derivatives such as mixed phthalic acid esters of higher alcohols (particularly phthalic acid esters); tris (2-ethylhexyl) ) Trimellitic acid derivatives such as trimellitate, tri (n-octyl) trimellitate, triisooctyl trimellitate (especially trimellitic ester); bis (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, mixed with higher alcohol Adipic acid derivatives such as adipic acid ester (especially adipic acid ester); Azelain such as bis (2-ethylhexyl) azelate, diisooctylazelate, di- (n-hexyl) azelate Derivatives (especially azelaic acid esters); Sebacic acid derivatives such as bis (2-ethylhexyl) sebacate and diisooctyl sebacate (especially sebacic acid esters); Sulphonic acid derivatives such as phenolic alkyl sulfonic acid esters (particularly sulfone) Acid ester); plasticizers such as epoxy derivatives such as epoxidized soybean oil and epoxidized linseed oil (especially epoxidized ester); dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, phthalic acid, ethylene glycol, A polyester plasticizer that is a polymerization ester with a dihydric alcohol such as propylene glycol or butylene glycol can be used. Among these plasticizers, a high molecular weight plasticizer is preferable from the viewpoints of migration, extractability, bleeding, and the like. In addition, a plasticizer may be used individually by 1 type, or may use 2 or more types together.

  The added amount of the plasticizer is about 10 to 100 parts by mass, preferably about 20 to 80 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. If the amount added is less than 10 parts by mass, the melt viscosity is high, the moldability when forming a sheet-like product is deteriorated, and the molded product is brittle and easily broken, which is not preferable. On the other hand, when the added amount exceeds 100 parts by mass, the flame retardancy of the molded body is lowered and the amount of smoke generated during combustion is increased, which is not preferable.

<Thermally expandable graphite>
The heat-expandable graphite constituting the heat-expandable vinyl chloride resin material of the present invention, for example, as a heat-expandable sheet, when placed in a space such as a window frame, causes the sheet to rise due to a temperature rise during a fire or the like. It becomes a foaming component for expanding. Thermally expandable graphite is a neutralized product by inserting a compound between layers of naturally produced scaly graphite. The compound contained by heat generates gas, and as a result, scaly graphite expands. To do.

  According to the study by the present inventors, the ratio of the thermally expandable graphite to the vinyl chloride resin is not an important factor, but if it is too large, the density of the expanded body after heating and expansion becomes small, and if it is too large, the expansion ratio Is small and does not play a role in preventing the spread of fire. The expansion ratio is calculated by the ratio of the vertical height of the expanded body after heating at 800 ° C. with the thickness before the test, and is preferably 10 to 40 times. In order to obtain this range, in the present invention, the number of blended parts of thermally expandable graphite is 50 to 150 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

  Scalar graphite powder produced in nature is made from inorganic acids such as concentrated sulfuric acid, nitric acid and selenic acid, or organic acids such as acetic acid and formic acid, concentrated nitric acid, perchloric acid, perchlorate and permanganate. In addition, it is preferable to treat it with a strong oxidizing agent such as dichromate or hydrogen peroxide. The graphite treated as described above is preferably neutralized with, for example, ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound, or the like.

  In order to prevent the spread of fire at the beginning of fire, it is necessary to start expansion of the thermally expandable graphite at a low temperature. For this reason, it is considered that when a low-temperature expandable one having an expansion start temperature of 180 to 240 ° C. is used, the vinyl chloride resin is entangled like a reinforcing material in the expanding heat-expandable graphite. Thus, a thermally expandable vinyl chloride resin material having a performance capable of effectively exerting a flame and smoke blocking function from a low temperature range can be obtained. For this reason, the heat-expandable sheet provided by the present invention exhibits the effect of preventing the spread of fire at an earlier stage in the early stage of the fire.

  The heat-expandable graphite used in the present invention preferably has an average particle size in the range of 100 to 600 μm, and more preferably in the range of 120 to 500 μm. When the average particle diameter satisfies such a range, the expansibility, workability, and shape retention are good.

  As described above, the amount of thermally expandable graphite added is about 50 to 150 parts by mass, and more preferably 70 to 100 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. If the amount added is too small, the flame retardant effect due to expansion cannot be obtained sufficiently. If the amount is too large, molding of the resin material becomes difficult, and the shape retention when foamed (expanded) is deteriorated.

<Other optional components>
(Heat stabilizer)
When molding the vinyl chloride resin material of the present invention, it is preferable to add a heat stabilizer in order to suppress thermal decomposition. As the heat stabilizer, for example, those generally used for hard vinyl chloride resins such as Pb-based or Sn-based, Ba / Zn composite, or Ca / Zn composite can be used. These heat stabilizers may be used alone or in combination of two or more. Moreover, the addition amount in the case of adding this heat stabilizer is about 0.1-10 mass parts with respect to 100 mass parts of vinyl chloride resin, More preferably, it is about 0.5-5 mass parts. .

(Modifier)
Further, in order to improve moldability and physical properties when forming a thermally expandable sheet using the thermally expandable vinyl chloride resin material of the present invention, an acrylic processing aid, acrylonitrile- Butadiene-styrene copolymer (ABS resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), acrylic polymers, modifiers such as chlorinated polyethylene, and the like within a range not impairing the effects of the present invention. It may be added.

(Foaming agent)
Further, in order to increase foamability (expandability), as an auxiliary foaming agent, for example, azo compounds such as azodicarbonamide, hydrazine compounds such as 4,4′-oxybis (benzenesulfonylhydrazide), N, N′-di Nitroso compounds such as nitrosopentamethylenetetramine, bicarbonates such as sodium bicarbonate, and the like may be added.

  In the present invention, it is possible to use a filler composed of an inorganic compound other than those specified in the present invention, if necessary, as long as the effects of the present invention are not impaired. Is preferably reduced.

  As other inorganic fillers that can be added as necessary, conventionally known ones listed below can be used. For example, metal oxides such as alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrites; hydrous inorganic substances such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and hydrotalcite; Metal carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, barium carbonate; calcium salts such as calcium sulfate, gypsum fiber, calcium silicate; silica, diatomaceous earth, dawn night, barium sulfate, talc , Clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica-based balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber Carbon balun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powders, slag fiber, fly ash, dehydration A sludge etc. can be mentioned.

<Method for producing thermally expandable vinyl chloride resin material>
In the method for producing the thermally expandable vinyl chloride resin material of the present invention, the expansion start temperature of 180 to 240 ° C. is 50 to 150 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. And, further, a dehydrochlorination catalyst for promoting dehydrochlorination of the vinyl chloride resin at the expansion start temperature, a dehydrochlorination inhibitor compound for suppressing dehydrochlorination, and a plasticizer for the vinyl chloride resin. Is used to produce a thermally expandable vinyl chloride resin material. Then, as described above, at that time, the type of the substance that becomes the dehydrochlorination catalyst and the determination of the addition amount are determined as prescribed in the present invention, and the dehydrochlorination catalyst used in combination with the dehydrochlorination catalyst is selected. As the hydrochloric acid inhibiting compound, a compound having an amino group and / or an ammonium group having a function of inhibiting the catalytic function of the dehydrochlorination catalyst at a heated initial temperature of 160 to 240 ° C. is used.

(Method for preparing resin material)
The thermally expandable vinyl chloride resin material of the present invention kneads the above-described components essential in the present invention and optional components to be added as necessary, for example, using a kneader such as a dissolver mixer or a kneader mixer. Can be obtained. The kneading is preferably performed so that the temperature of the resin material in the kneading apparatus is 20 to 50 ° C. Depending on the method of forming the thermally expandable sheet after that, for example, if the thermally expandable sheet is formed by the comma coat molding method, the thermally expandable vinyl chloride resin material should be made into a suitable paste. Therefore, it is preferable to adjust so that the viscosity at 25 ° C. is about 5000 to 20000 mPa · sec. A solvent can be added to this resin material to make it into a paste and used as a putty. In addition, it is used as a paint (coating agent) by using a suitable amount of a solvent having affinity for vinyl chloride resin to form a paint. Examples of the solvent having affinity for the vinyl chloride resin include tetrahydrofuran and toluene.

<Method of forming thermally expandable sheet>
The thermally expandable vinyl chloride resin material of the present invention can be easily molded into a thermally expandable sheet by using, for example, a simple comma coat molding method. By coating a paste-like thermally expandable vinyl chloride resin material on a releasable base material (base paper), a sheet having an appropriate thickness can be easily obtained. The thermally expandable sheet of the present invention is preferably about 0.5 mm to 2.0 mm, but can be easily obtained by applying the comma coat molding method using the thermally expandable vinyl chloride resin material of the present invention. It is done. At this time, unlike the case of producing a heat-expandable sheet by extrusion molding or calender molding, it is not necessary to melt the resin material with heat and pressure, so the shrinkage when the sheet generated in these methods is cooled. Problems are suppressed and a uniform sheet in good condition is obtained.

(Thermal expansion sheet)
The thermally expandable sheet obtained from the thermally expandable vinyl chloride resin material of the present invention can be easily obtained by comma-coating the above-described thermally expandable vinyl chloride resin material. The heat-expandable sheet of the present invention expands by being heated to an expansion temperature (usually 180 ° C.) or higher with a flame by a gas burner or the like, hot air, or the like. The expansion body expanded by heat not only can retain its shape by itself, but also has sufficient mechanical strength to block the flame and smoke. Therefore, by using the thermally expandable sheet of the present invention for a window frame (for example, between a sash and a wall) of a building such as a house or a building, the molded body does not burn even in the event of a fire, etc. The flame can be prevented from propagating to the back surface. The heat-expandable sheet of the present invention can be used in other applications where fire resistance such as gaps such as fire doors is required or where fire protection is necessary.

  The method of measuring the cohesive strength of the expanded body after the high-temperature combustion test at 800 ° C. used for evaluating the function of the thermally expandable vinyl chloride resin material of the present invention is not a method shown by an official method, but an in-house method. I went there. Specifically, a sample having a thickness of 1.5 to 1.6 mm and a surface area of 20 mm × 20 mm is prepared from a heat-expandable vinyl chloride resin material, and the expanded body obtained after heating at 800 ° C. A flat plate at the top was pushed down by a compression tester or the like, and the maximum drag measured from the bottom to a height of 8 mm was indicated by kgf.

  Next, the present invention will be described in more detail with reference to study examples, examples, and comparative examples. The present invention is not limited in any way by these examples. In the text, “part” or “%” is based on mass unless otherwise specified.

The main components used in the study examples, examples and comparative examples are as follows. Both zinc oxide and iron chloride used for the dehydrochlorination catalyst are sold as reagents. Substances used to determine whether they fall under the dehydrochlorination inhibiting compound will be described later.
-Vinyl chloride resin As the vinyl chloride resin, Leuron paste 772A (trade name) manufactured by Tosoh Corporation having an average degree of polymerization of 1,650 was used. Hereinafter, it may be abbreviated as PVC.
-Plasticizer Dioctyl phthalate (manufactured by Shin Nippon Rika Co., Ltd., Sunsocizer DOP (trade name)), which is a plasticizer for vinyl chloride resin, was used. Hereinafter, it may be abbreviated as DOP.
-Thermally expandable graphite SYZR802 (trade name) manufactured by Sanyo Trading Co., Ltd. having an expansion start temperature of 180 ° C. and an average particle diameter of 180 μm was used as the thermally expandable graphite.
-Thermal stabilizer The composite material of Zn / Ca was used for the thermal stabilizer. Specifically, Daikyo Kasei Co., Ltd. LX-550 was used.

[Examination example 1]-Example of selection method of dehydrochlorination catalyst As shown in Table 1, heat-expandable graphite and typical ammonium polyphosphate as a flame retardant are used, and zinc oxide or calcium carbonate is added to this. Thus, a thermally expandable vinyl chloride resin material was prepared. And the graph of the foaming ratio at the time of heating the 2 types of preparations prepared above to 800 degreeC in FIG. 5 was shown. From any of the compositions shown in FIG. 5, the expansion starts from 200 ° C., which is the expansion start temperature of the thermally expandable graphite, and the foaming progresses rapidly. From the temperature of about 500 to 600 ° C., the foaming speed decreases. Recognize.

  On the other hand, as a result of measuring the cohesive strength by the following method using the two types of thermally expandable vinyl chloride resin materials prepared, the cohesive strength was as high as 1.22 kgf when zinc oxide was added. On the other hand, in the case of adding calcium carbonate, it was as low as 0.38 kgf. Here, the zinc oxide is defined by adding 5.2 parts by mass of zinc oxide as a dehydrochlorination catalyst to 52 parts by mass of a vinyl chloride resin and 42.8 parts by mass of a plasticizer as defined in the present invention. When the sample A is heated at 180 ° C. for 15 minutes and then at 190 ° C. for 15 minutes, the weight loss of the sample A is 45% by mass (residual amount remaining amount is 55%). On the other hand, the calcium carbonate is a sample A formulated by adding 5.2 parts by mass of calcium carbonate to 52 parts by mass of a vinyl chloride resin and 42.8 parts by mass of a plasticizer as defined in the present invention. When heated at 180 ° C. for 15 minutes and then at 190 ° C. for 15 minutes, the weight loss of the sample A was 3% by mass (the remaining amount of residue was 97%), which is the expansion start temperature of the thermally expandable graphite. It is a substance that hardly loses weight at low temperatures.

  These facts show that the caking force of the heated expansion body can be increased by using a compound such as zinc oxide that has a large weight loss of sample A. In the present invention, such a substance is called a dehydrochlorination catalyst. Details of this point are described in Patent Document 2 described above. As described in Patent Document 2, as the dehydrochlorination catalyst, the use of a compound having a large weight loss of the sample A defined in the present invention, such as the above-described zinc oxide, allows the heating expanded body to be caking. You can increase your power. Examples of the other substances include metal zinc, zinc carbonate, zinc chloride, and iron chloride. However, the substance is limited to these as long as the substance is applicable for the purpose of reducing the weight of sample A defined in the present invention. Any material can be used without any modification.

  The caking force is a heat-expandable vinyl chloride resin material obtained as described above, and a sheet-like sample having a thickness of 1.5 to 1.6 mm and a surface area of 20 × 20 mm is prepared. Apply a smooth plate to the top of the heated expansion body obtained by heating to 800 ° C., and then press down the plate with a compression tester until the plate reaches a height of 8 mm from the bottom. Is the maximum drag measured in kgf.

[Examination Example 2] -Examination test for finding a dehydrochlorination inhibiting compound Zinc oxide was used as a dehydrochlorination catalyst, and various amino group-containing compounds and ammonium group-containing compounds described in Table 4 were added as dehydrochlorination inhibiting compounds. The heat-expandable vinyl chloride resin materials having the basic composition C shown in Table 2 were measured for the caking force of the heat-expandable bodies of the respective resin materials, and the heat expansion caused by adding these compounds. The influence on the caking power of the body was confirmed. As representative examples of the dehydrochlorination catalyst, zinc oxide and iron chloride were used, respectively. Table 2 shows the formulation when zinc oxide is used. Hereinafter, the case where zinc oxide is used will be described as an example.

  The reason why zinc oxide was used as a dehydrochlorination catalyst in the above-mentioned formulation C, and that the amount thereof was used at a ratio of 11.1 parts with respect to 100 parts of the polyvinyl chloride resin as a base is that zinc oxide is used in the present invention. When the sample A specified in 1 is heated at 180 ° C. for 15 minutes and then at 190 ° C. for 15 minutes, the weight loss of the sample A is 45% by mass (residual amount remaining amount is 55%) This is because the heated expansion body has a high caking force. In addition, the amount of zinc oxide added is a desired amount based on 52 parts by mass of vinyl chloride resin, 42.8 parts by mass of plasticizer and 100 parts by mass of vinyl chloride resin as defined in the present invention. The value determined on the basis of the value obtained for the sample B to which the dehydrochlorination catalyst was added, after being heated at 180 ° C. for 15 minutes and then at 190 ° C. for 15 minutes, the weight loss of the sample B being within 25% by mass or more It is. Table 3 shows the relationship between the amount of zinc oxide added and the weight loss in Sample B.

In the basic composition C shown in Table 2, liquids were prepared by changing the types of compounds to be studied for finding dehydrochlorination inhibiting compounds defined in the present invention. The coat was made to be 1.5 to 1.6 mm. Furthermore, a polyester nonwoven fabric having a density of 450 g / m ² was lightly laminated on the surface of the coating solution. Next, it is heated in a hot air drying oven at 190 to 195 ° C. for 3 to 5 minutes to produce laminates made by laminating the thermally expandable vinyl chloride resin material and the polyester nonwoven fabric, and releasing the release paper. Thus, a test sample was obtained.

  Each of the laminate samples obtained above was cut into a 20 × 20 mm area and heated. Prior to heating, the thickness of the laminate sample was measured. The laminate sample was heated to 800 ° C., and the expansion ratio and the cohesive strength were measured by the following methods for the heat expansion body obtained after the expansion by heating.

  The expansion ratio of each resin material was determined by measuring the vertical height of the heated expanded body obtained above and “vertical height of expanded body after test / thickness before test”. The caking force of the heated expanded body is determined by applying a smooth plate to the top of the heated expanded body obtained by heating each laminate sample obtained above to 800 ° C. and expanding the sample, and then pressing the plate with a compression tester. When pressed down, the maximum drag measured by the plate position from the bottom to a height of 8 mm is shown in kgf. The results obtained are shown in Table 4.

  About each laminated body sample obtained above, it cut out by the area of 5x10mm separately, respectively, was set as the sample for an elution test, and the weight of each sample was measured. Then, 5 samples were immersed in 100 g of purified water and left at 95 ° C. for 24 hours to conduct a dissolution test. After the test, it was taken out from the hot water and dried at 95 ° C. for 3 hours, and the weight after drying was measured. And the elution amount by hot water was computed from the weight before throwing into hot water, and the weight after drying, and the weight loss ratio with respect to before feed was displayed in% and made water resistance. The results obtained are shown in Table 4.

Table 4 shows the overall judgment results, and the criteria are as follows.
(Double-circle): The caking force of a heating expansion body is 1.0 kgf or more, and the weight loss rate which shows water resistance is 2.5% or less.
○: The caking force of the heated expanded body is 1.0 kgf or more, and the weight loss ratio indicating water resistance is more than 2.5% to 7.5% or less.
(Triangle | delta): The caking force of a heating expansion body is 1.0 kgf or more, and the weight loss rate which shows water resistance is more than 7.5%.
X: The caking force of a heating expansion body is less than 1.0 kgf.

  As shown in Table 4, the cohesive strength of the heated expansion body clearly shows that when a compound containing an amino group or an ammonium group is added to the structure, a compound having no such group is added. It was confirmed that a high value was shown compared with the case of using. Moreover, as shown in Table 4, when melamine is used, the foaming ratio shows a very high numerical value, and when a compound having a structure having an amino group is used, the heating expansion body has a very high foaming ratio. Nevertheless, it was found that a high caking force can be realized. From this, the present inventors combined the dehydrochlorination catalyst such as zinc oxide, and the cohesive strength of the heated expanded body when using melamine having an amino group in its structure is the expansion ratio. It is expected to be even higher if it is suppressed to the same extent as other compounds.

  In the case of methylol melamine, which is a melamine that does not have an amino group in the structure, high caking force cannot be realized in the heated expanded body, and from this also, a dehydrochlorination catalyst such as zinc oxide In combination with the “compound having an amino group and / or an ammonium group” defined in the present invention. As shown in Table 2, what was determined as a compound in which the resin material was excellent in water resistance and the cohesive strength of the heat-expanded body was high, as a result of the comprehensive determination, was melamine polyphosphate, melam melem, Melamine cyanurate and melamine polyphosphate. Although combined with a dehydrochlorination catalyst such as zinc oxide, the heat-expandable body has high cohesive strength, but the compounds that resulted in slightly poor water resistance of the resin materials are ammonium polyphosphate, melamine sulfate, benzoguanamine, melamine And silane-coated ammonium polyphosphate. Although the water resistance of the resin material is inferior, the cohesive strength of the heated expanded body is made higher than before by using a dehydrochlorination catalyst in combination with the “compound having an amino group and / or ammonium group” defined in the present invention. I was able to confirm that it was possible. Although this is subject to the restriction that rainwater etc. will not be applied to the place of use, if you keep this in mind, using it as a fire spread prevention material that causes expansion by heat at the time of fire and slows down the fire Means useful.

[Examination example 3]-Confirmation about the effect of using together a dehydrochlorination catalyst and "compound which has an amino group and / or an ammonium group" In the basic compounding C used in the examination example 2, with respect to 27.0 parts of PVC As a dehydrochlorination catalyst, 3.0 parts of zinc oxide or 3.0 parts of iron chloride is used, and “a compound having an amino group and / or ammonium group” is used as a compound having 20 parts of ammonium polyphosphate or melamine. In this example, when these compounds were not blended, each thermally expandable vinyl chloride resin material was blended and evaluated when only one of them was blended. The evaluation was performed in the same manner as described above by measuring the foaming ratio of the resin material and the caking force of the heated expansion body. Table 5 shows the difference in formulation and the measurement results.

[Examination example 4]-Confirmation test of effect by using dehydrochlorination inhibiting compound in combination The test sample obtained by peeling the release paper prepared in Examination example 2 was cut into a predetermined size of 20 x 20 mm. Each specimen was measured, and the weight of the obtained specimen was measured. Then, each test body was put in the hot air dryer, and the heat loss was measured. Specifically, for the case where the temperature in the hot air dryer is set to 160 ° C., 190 ° C., 220 ° C., 240 ° C., which is a temperature assuming the rising portion of the expansion start temperature range of the thermally expandable graphite, 10 minutes each. Each weight measurement was carried out for 60 minutes, the remaining rate (%) was obtained, and the respective results were displayed in graphs in FIGS. As a result, surprisingly, in the result of heating at 160 ° C. and 190 ° C. shown in FIG. 1 and FIG. In the thermally expandable vinyl chloride resin material to which the “amino group-containing compound and / or ammonium group-containing compound” is added, the residual ratio is high, and the caking force of the heat expansion body is low. It was confirmed that an additive having neither an amino group nor an ammonium group in the structure shows a rapid decrease in the remaining ratio as the heating time elapses. On the other hand, as shown in FIG.3 and FIG.4, when reaching 220 degreeC and 240 degreeC, in any case, the monotonous weight loss curve was shown.

  These results seem to be inconsistent with the results of the examination example 1 in the method of selecting a dehydrochlorination catalyst, in which a substance whose weight is severely reduced by heating at a low temperature has the effect of increasing the cohesive strength of the heated expansion body. doing. However, considering the results obtained in FIGS. 1 to 4 and the effect of addition of the dehydrochlorination catalyst obtained in Study Example 3, the present inventors infer as follows.

  In order to increase the cohesive strength of the heated expanded body, the vinyl chloride resin component needs to be sufficiently clinged to the thick fiber-shaped graphite expanded body that is developed in accordance with the expansion of the graphite. It is considered that it is difficult to generate a resin component mixing effect if the amount of drastic reduction in this expansion start temperature region, that is, dehydrochlorination progresses too rapidly. In contrast, as shown in FIGS. 1 and 2, dehydrochlorination proceeds rapidly due to the presence of the “amino group-containing compound and / or ammonium group-containing compound” having a function of suppressing the catalytic function of the dehydrochlorination catalyst. It is inferred that the generated hydrochloric acid is supplemented and plays a role in preventing the zipper effect.

  From the results of FIGS. 3 and 4, it is considered that when the temperature is subsequently increased, the catalytic effect of dehydrochlorination becomes dominant over the effect of suppressing dehydrochlorination in the stage where the rapid rise region of expansion has passed. Alternatively, it is considered that the amino group and the ammonium group completely absorb the generated hydrochloric acid and lose the zipper blocking effect. At subsequent temperatures, the dehydrochlorination catalyst works sufficiently to advance carbonization of the vinyl chloride resin. At this stage, since the resin component is already clinging to the expandable fiber, the carbonization proceeds while being bound to each other, and this is considered to have produced a good caking force. In addition, the above is inference from the obtained phenomenon, and has not been fully elucidated yet.

[Examination Example 5] -Confirmation of the influence on the caking force of the heated expanded body when the addition amount of the amino group-containing compound of Formulation C is changed

  From the results of Table 6, it was confirmed that the caking force of the heated expanded body increases as the number of added amino group-containing compounds increases. Further, it was found that the addition amount was almost saturated at 15 to 20 parts. Further, when the amount is 20 parts or more, the processing characteristics deteriorate, so the amount is preferably about 20 parts.

  If the contribution of the amino group-containing compound to the caking force is due to the removal of hydrochloric acid generated by a dehydrochlorination catalyst such as zinc oxide from the system, the influence of the number of amino groups contained in the compound is affected. Will receive. Although it is not clarified from Table 6, the influence on the caking force of the heated expansion body, which is probably caused by the number of added parts, is based on it. It is estimated to add to the effect of hydrochloric acid catalyst.

[Examination Example 6] -Confirmation of the influence on the caking force of the heated expansion body when the addition amount of the amino group-containing compound of Formulation C is made constant and the addition amount of zinc oxide is changed.

  From the results in Table 7, it was confirmed that the caking force increases as the number of added parts of zinc oxide increases. In the case of this composition, it was confirmed that it was saturated at about 75% of the standard. This phenomenon indicates the presence of a saturated amount in the same tendency as in Table 3 showing the relationship between the amount of zinc oxide added and the remaining heating amount (%).

Claims (12)

Thermal expansion comprising a vinyl chloride resin, a plasticizer for the resin, thermally expandable graphite having an expansion start temperature of 180 to 240 ° C., a dehydrochlorination catalyst for the vinyl chloride resin, and a dehydrochlorination inhibitor compound. A vinyl chloride resin material,
In 100 parts by mass of the vinyl chloride resin, the thermally expandable graphite is included in a range of 50 to 150 parts by mass,
The dehydrochlorination catalyst comprises 52 parts by mass of a vinyl chloride resin having an average degree of polymerization of 400 to 3000, 42.8 parts by mass of dioctyl phthalate as a plasticizer for the resin, and 5.2 parts by mass of a dehydrochlorination catalyst. Part A is a substance in which the weight loss of the sample A is 25% by mass or more when the sample A having a composition added is heated at 180 ° C. for 15 minutes and then at 190 ° C. for 15 minutes, and
The addition amount of the dehydrochlorination catalyst to 100 parts by mass of the vinyl chloride resin is 52 parts by mass of a vinyl chloride resin having an average degree of polymerization of 400 to 3000, and dioctyl phthalate which is a plasticizer for the resin Sample B, to which 42.8 parts by mass and further a desired amount of dehydrochlorination catalyst with respect to 100 parts by mass of the vinyl chloride resin having an average degree of polymerization of 400 to 3000, was added at 180 ° C. for 15 minutes, then 190 After heating at 15 ° C. for 15 minutes, the weight loss of the sample B is within a range of 25% by mass or more,
The dehydrochlorination inhibiting compound is a compound having an amino group and / or an ammonium group having a function of inhibiting the catalytic function of the dehydrochlorination catalyst at a heated initial temperature of 160 to 240 ° C.
A heat-expandable vinyl chloride-based resin material, wherein the expanding body obtained by heating at 800 ° C. has a caking strength of 0.8 kgf or more.   The dehydrochlorination inhibitor is melamine polyphosphate, melamine polyphosphate, melam, melem, melamine phosphate, melamine polyphosphate metal salt, piperazine phosphate, ethylenediamine phosphate, melamine sulfate, melamine, melam, melem, melamine cyanurate 2. The thermally expandable vinyl chloride resin material according to claim 1, which is at least one selected from the group consisting of benzoguanamine, silane-coated ammonium polyphosphate, melamine-coated ammonium polyphosphate, urea, and ammonium chloride.   2. The dehydrochlorination inhibiting compound is at least any one selected from the group consisting of melamine polyphosphate, melamine / melam / melem polyphosphate, melamine cyanurate, melamine sulfate, melamine, benzoguanamine, and silane-coated ammonium polyphosphate. The heat-expandable vinyl chloride resin material described in 1.   The thermally expansible vinyl chloride according to any one of claims 1 to 3, wherein the amount of the dehydrochlorination inhibiting compound used is in the range of 50 to 150 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. Resin material.   The thermally expandable vinyl chloride resin material according to any one of claims 1 to 4, wherein an elution amount when immersed in hot water at 95 ° C for 24 hours is 2.5% or less on a mass basis. It is obtained by heating at 800 ° C. a test piece obtained by laminating and laminating a polyester nonwoven fabric with a density of 300 g / m ^{2 on} a layer having a thickness of 1.5 to 1.6 mm and an area of 20 × 20 mm formed by a resin material. The heat-expandable vinyl chloride resin material according to any one of claims 1 to 5, wherein the expanding body has a caking force of 1.0 kgf or more.   The heat according to any one of claims 1 to 6, wherein the dehydrochlorination catalyst is at least one selected from the group consisting of zinc metal, zinc oxide, zinc carbonate, zinc chloride, copper, copper oxide, and iron chloride. Expandable vinyl chloride resin material.   The thermally expandable vinyl chloride resin material according to any one of claims 1 to 7, wherein the shape is a sheet shape and the thickness is 0.5 mm to 2.0 mm.   The thermally expandable vinyl chloride resin material according to any one of claims 1 to 7, wherein the shape is paste or paint.   The thermally expandable vinyl chloride resin material according to claim 8 or 9, which is for installation on a window frame or a door frame. A method for producing a thermally expandable vinyl chloride resin material,
Thermal expansion graphite having an expansion start temperature of 180 to 240 ° C. is used in the range of 50 to 150 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, and the vinyl chloride resin at the expansion start temperature. A dehydrochlorination catalyst for promoting dehydrochlorination, a dehydrochlorination inhibiting compound for inhibiting dehydrochlorination, and a plasticizer for the vinyl chloride resin, and a thermally expandable vinyl chloride containing them When manufacturing the resin material
The dehydrochlorination catalyst is composed of 52 parts by mass of a vinyl chloride resin having an average degree of polymerization of 400 to 3000, 42.8 parts by mass of dioctyl phthalate as a plasticizer for the resin, and 5.2 parts by mass of a dehydrochlorination catalyst. When the sample A having a composition added partly is heated at 180 ° C. for 15 minutes and then at 190 ° C. for 15 minutes, the sample A is selected from substances whose weight loss is 25% by mass or more, and
The addition amount of the dehydrochlorination catalyst with respect to 100 parts by mass of the vinyl chloride resin, 52 parts by mass of vinyl chloride resin having an average degree of polymerization of 400 to 3000, and dioctyl phthalate which is a plasticizer for the resin Sample B, to which 42.8 parts by mass and further a desired amount of dehydrochlorination catalyst with respect to 100 parts by mass of the vinyl chloride resin having an average degree of polymerization of 400 to 3000, was added at 180 ° C. for 15 minutes, then 190 After heating for 15 minutes at ° C., the weight loss of the sample B is determined to be within a range of 25% by mass or more,
Further, as the dehydrochlorination suppressing compound, a compound having an amino group and / or an ammonium group having a function of suppressing the catalytic function of the dehydrochlorination catalyst at a heated initial temperature of 160 to 240 ° C. is used. A method for producing a heat-expandable vinyl chloride resin material.   The dehydrochlorination inhibitor is melamine polyphosphate, melamine polyphosphate, melam, melem, melamine phosphate, melamine polyphosphate metal salt, piperazine phosphate, ethylenediamine phosphate, melamine sulfate, melamine, melam, melem, melamine cyanurate The method for producing a thermally expandable vinyl chloride resin material according to claim 11, which is at least one selected from the group consisting of benzoguanamine, silane-coated ammonium polyphosphate, melamine-coated ammonium polyphosphate, urea, and ammonium chloride.

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