WO2022024490A1

WO2022024490A1 - Foamable composition and foam body

Info

Publication number: WO2022024490A1
Application number: PCT/JP2021/017750
Authority: WO
Inventors: 寿雄佐藤; 博行石黒; 貴史砂田
Original assignee: デンカ株式会社
Priority date: 2020-07-31
Filing date: 2021-05-10
Publication date: 2022-02-03
Also published as: KR20230045589A; JPWO2022024490A1

Abstract

A foamable composition containing a chloroprene polymer, wherein formula (A) is satisfied between the maximum value X (unit: dN·m) of torque in a vulcanization curve of the foamable composition measured at 150°C and the mooney viscosity Y of the foamable composition measured after a preheating time of 1 minute at 100°C and a measurement time of 4 minutes. A foam body of the foamable composition.　(A): Y≤-1.33X+30.67

Description

Effervescent compositions and foams

The present invention relates to an effervescent composition, a foam, and the like.

The foam can be used for various purposes such as buildings, automobiles, electrical equipment, and audio equipment. As an effervescent composition for obtaining a foam, a composition containing polypropylene or the like is known (see, for example, Patent Document 1 below).

Japanese Unexamined Patent Publication No. 2018-119089

The foamable composition for obtaining a foam is required to have a high foaming ratio from the viewpoint of efficiently obtaining a foam having a low specific gravity.

One aspect of the present invention is to provide an effervescent composition having a high effervescence ratio. Another aspect of the invention is to provide a foam of such an effervescent composition.

One aspect of the present invention is an effervescent composition containing a chloroprene polymer, which has a maximum torque value X (unit: dN · m) in the vulcanization curve of the effervescent composition measured at 150 ° C. , The Mooney viscosity Y of the effervescent composition measured at 100 ° C. with a preheating time of 1 minute and a measurement time of 4 minutes satisfies the following formula (A).
Y ≤ -1.33X + 30.67 ... (A)

Such an effervescent composition has a high effervescence ratio. Thereby, a foam having a low specific density can be efficiently obtained.

Another aspect of the present invention relates to the foam of the above-mentioned effervescent composition.

According to one aspect of the present invention, it is possible to provide an effervescent composition having a high effervescence ratio. According to another aspect of the present invention, it is possible to provide a foam of such an effervescent composition.

It is a figure which shows the relationship between the maximum value X of torque and Mooney viscosity Y.

Hereinafter, embodiments for carrying out the present invention will be described in detail. The present invention is not limited to the embodiments described below.

In the present specification, "A or more" in the numerical range means A and a range exceeding A. "A or less" in the numerical range means A and a range less than A. Within the numerical range described stepwise herein, the upper or lower limit of the numerical range at one stage may be optionally combined with the upper or lower limit of the numerical range at another stage. In the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. "A or B" may include either A or B, and may include both. Unless otherwise specified, the materials exemplified in the present specification may be used alone or in combination of two or more. The content of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. The term "process" is included in this term not only in an independent process but also in the case where the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. By "(meth) acrylic acid" is meant at least one of acrylic acid and the corresponding methacrylic acid. The same applies to other similar expressions such as "(meth) acrylate".

The effervescent composition according to this embodiment contains a chloroprene polymer. In the effervescent composition according to the present embodiment, the maximum value X (unit: dN · m) of the torque (vulcanization torque) in the vulcanization curve of the effervescent composition measured at 150 ° C. and preheating at 100 ° C. The Mooney viscosity Y (ML _{1 + 4} ) of the effervescent composition measured at an hour of 1 minute and a measurement time of 4 minutes satisfies the following formula (A).
Y ≤ -1.33X + 30.67 ... (A)

The effervescent composition according to this embodiment has a high effervescence ratio. Thereby, a foam having a low specific density can be efficiently obtained. For example, according to the effervescent composition according to the present embodiment, a sheet of the effervescent composition having a length of 20 mm, a width of 20 mm, and a thickness of 3 mm was foamed at 150 ° C. for 20 minutes and then held at 25 ° C. for 30 minutes. In some cases, a foaming ratio of 600% (volume%) or more ([(volume after foaming-volume before foaming) / volume before foaming] × 100) can be obtained. When the purpose is not to evaluate the foaming ratio, a foam may be obtained under conditions other than the above conditions.

The above-mentioned foaming ratio is 650% or more, 700% or more, 750% or more, 800% or more, 850% or more, 900% or more, 950% or more, 1000% or more, 1050% or more, or 1110% or more. good. The foaming ratio may be, for example, 1500% or less.

The foam according to the present embodiment is a foam obtained by foaming the foamable composition according to the present embodiment, and is a foam of the foamable composition according to the present embodiment. The foam according to this embodiment can have suitable softness. The hardness of the foam according to the present embodiment (Asker F hardness) may be in the following range. The hardness of the foam may be less than 80, 75 or less, 70 or less, 65 or less, 60 or less, 55 or less, or 50 or less. The hardness of the foam may be 1 or more, 5 or more, 10 or more, 15 or more, or 20 or more. The hardness of the foam can be measured by the procedure described in Examples.

The maximum torque value X can be obtained from the vulcanization curve of the effervescent composition measured at 150 ° C. in accordance with ISO 6502 (ASTM D5289). ISO 6502 (ASTM D5289) corresponds to JIS K6300-2: 2001. The vulcanization curve can be obtained using a rheometer and can be obtained by measuring at 150 ° C. for 20 minutes.

The maximum torque value X may be in the following range from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having suitable softness. The maximum torque value X is 1.0 dN ・ m or more, 3.0 dN ・ m or more, 5.0 dN ・ m or more, 8.0 dN ・ m or more, 9.0 dN ・ m or more, 9.9 dN ・ m or more, 10 .0dN ・ m or more, 11.0dN ・ m or more, 11.5dN ・ m or more, 12.0dN ・ m or more, 12.5dN ・ m or more, 13.0dN ・ m or more, 13.5dN ・ m or more, 14. 0dN ・ m or more, 14.5dN ・ m or more, 15.0dN ・ m or more, 15.5dN ・ m or more, 16.0dN ・ m or more, 16.5dN ・ m or more, 17.0dN ・ m or more, 17.5dN It may be m or more, 18.0 dN · m or more, or 18.5 dN · m or more. The maximum torque value X is 30.0 dN ・ m or less, 25.0 dN ・ m or less, 21.0 dN ・ m or less, 20.5 dN ・ m or less, 20.0 dN ・ m or less, 19.0 dN ・ m or less, 18 .5dN ・ m or less, 18.0dN ・ m or less, 17.5dN ・ m or less, 17.0dN ・ m or less, 16.5dN ・ m or less, 16.0dN ・ m or less, 15.5dN ・ m or less, 15. 0dN ・ m or less, 14.5dN ・ m or less, 14.0dN ・ m or less, 13.5dN ・ m or less, 13.0dN ・ m or less, 12.5dN ・ m or less, 12.0dN ・ m or less, 11.5dN It may be m or less, 11.0 dN · m or less, 10.0 dN · m or less, 9.9 dN · m or less, or 9.5 dN · m or less. From these viewpoints, the maximum torque values X are 1.0 to 30.0 dN ・ m, 5.0 to 20.0 dN ・ m, 8.0 to 18.0 dN ・ m, 9.0 to 15.0 dN ・. It may be m, 9.0 to 13.0 dN · m, or 9.0 to 12.0 dN · m. The maximum torque value X tends to increase as the content of the filler increases. As the content of the plasticizer or foaming agent increases, the maximum torque value X tends to decrease.

The Mooney viscosity Y may be in the following range from the viewpoint of easily obtaining a high foaming ratio and the viewpoint of easily obtaining a foam having suitable softness. Mooney viscosity Y is 0 or more, 0 or more, 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, 10 or more, 11 or more, 12 or more, or 13. It may be the above. The Mooney viscosity Y may be 20 or less, 15 or less, 13 or less, 12 or less, 11 or less, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, or 3 or less. From these viewpoints, the Mooney viscosity Y may be 0 to 20, 1 to 10, 2 to 9, 2 to 8, or 3 to 6. The Mooney viscosity Y of the effervescent composition tends to increase as the content of the filler increases. The Mooney viscosity Y of the effervescent composition tends to decrease as the content of the plasticizer or the frothing agent increases.

The chloroprene polymer is a polymer having a structural unit derived from chloroprene (2-chloro-1,3-butadiene) (a polymer having chloroprene as a monomer unit). The chloroprene polymer may be a homopolymer of chloroprene; a copolymer of chloroprene and another monomer copolymerizable with chloroprene, or the like. The polymer structure of the chloroprene polymer is not particularly limited.

The content of the structural unit derived from chloroprene is 50% by mass or more and 70% by mass based on the total mass of the chloroprene polymer from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having suitable softness. % Or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 99% by mass or more. The chloroprene polymer may be an embodiment consisting of a structural unit derived from chloroprene (a mode in which substantially 100% by mass of the chloroprene polymer is a structural unit derived from chloroprene).

As monomers copolymerizable with chloroprene, esters of (meth) acrylates (methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc.), hydroxyalkyl (meth). ) Acrylate (2-hydroxyethyl (meth) acrylate, 2-hydroxymethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc.), 2,3-dichloro-1,3-butadiene, 1-chloro-1 , 3-butadiene, butadiene, isoprene, ethylene, styrene, acrylonitrile and the like. The other monomer copolymerizable with chloroprene is not limited to one kind, and for example, three or more kinds of monomers containing chloroprene may be copolymerized.

Even if the chloroprene polymer is a sulfur-modified chloroprene polymer, a mercaptan-modified chloroprene polymer, a xanthogen-modified chloroprene polymer, a dithiocarbonate-based chloroprene polymer, a trithiocarbonate-based chloroprene polymer, a carbamate-based chloroprene polymer, or the like. good. The chloroprene polymer may contain a sulfur-modified chloroprene polymer from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having suitable softness.

The sulfur-modified chloroprene polymer does not have to have a structure represented by the following general formula (I) at the molecular terminal (R ¹ indicates an alkyl group having 1 to 4 carbon atoms).
-SC (= S) -OR ¹ ... (I)

The content of the chloroprene polymer is based on the total mass of the effervescent composition (total mass of solid content; the same applies hereinafter) from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having suitable softness. It may be in the following range. The content of chloroprene polymer is 50% by mass or more, more than 50% by mass, 55% by mass or more, 60% by mass or more, 65% by mass or more, 67% by mass or more, 68% by mass or more, 69% by mass or more, 70% by mass. % Or more, 71% by mass or more, 72% by mass or more, 73% by mass or more, 74% by mass or more, 75% by mass or more, 76% by mass or more, 77% by mass or more, or 78% by mass or more. The content of the chloroprene polymer is 90% by mass or less, 85% by mass or less, 80% by mass or less, 79% by mass or less, 78% by mass or less, 77% by mass or less, 76% by mass or less, 75% by mass or less, 74% by mass. % Or less, 73% by mass or less, 72% by mass or less, 71% by mass or less, 70% by mass or less, or 69% by mass or less. From these viewpoints, the content of the chloroprene polymer may be 50 to 90% by mass, 60 to 80% by mass, or 65 to 80% by mass.

The effervescent composition according to the present embodiment may contain a filler and may not contain a filler. Examples of the filler include carbon black, silica, clay, talc, calcium carbonate and the like. The filler may be free of at least one selected from the group consisting of silica, clay, talc and calcium carbonate. The filler may contain carbon black from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having a suitable softness.

Examples of carbon black include furnace black by incomplete combustion method; thermal black by thermal decomposition method; channel black; acetylene black and the like. The furnace black, HAF (High Abrasion Furnace Black), SAF (Super Abrasion Furnace Black), ISAF (Intermediate Super Abrasion Furnace Black), IISAF (Intermediate ISAF), MAF (Medium Abrasion Furnace Black), FEF (Fast Extruding Furnace Black ), SRF (Semi-Reinforcement Furnace Black), GPF (General Purpose Furnace Black), FF (Fine Furnace Black), CF (Conducive Furnace Black) and the like. Examples of the thermal black include FT (Fine Thermal Black) and MT (Medium Thermal Black). Examples of the channel black include EPC (Easy Processing Channel Black) and MPC (Medium Processing Channel Black). Examples of acetylene black include ACET (Acetylene Black) and the like. The carbon black may contain HAF from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having a suitable softness.

The content of the filler may be in the following range with respect to 100 parts by mass of the chloroprene polymer from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having suitable softness. The content of the filler is 10 parts by mass or less, less than 10 parts by mass, 8 parts by mass or less, 6 parts by mass or less, 5 parts by mass or less, 4 parts by mass or less, 3 parts by mass or less, 2 parts by mass or less, or 1 part. It may be less than or equal to a mass part. The content of the filler is 0 parts by mass or more and may exceed 0 parts by mass, and is 0.5 parts by mass or more, 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 4 parts by mass or more, or It may be 5 parts by mass or more. From these viewpoints, the content of the filler is 0 to 10 parts by mass, more than 0 parts by mass and 10 parts by mass or less, more than 0 parts by mass and 5 parts by mass or less, more than 0 parts by mass and 2 parts by mass or less, or. It may be 1 to 5 parts by mass. From the same viewpoint, the content of carbon black may be in each of the above ranges with respect to 100 parts by mass of the chloroprene polymer.

The content of the filler may be in the following range based on the total mass of the effervescent composition from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having suitable softness. The content of the filler is 10% by mass or less, 9% by mass or less, 8% by mass or less, 7% by mass or less, 6% by mass or less, 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass. Hereinafter, it may be 1% by mass or less, 0.8% by mass or less, 0.75% by mass or less, 0.72% by mass or less, or 0.7% by mass or less. The content of the filler is 0% by mass or more and may exceed 0% by mass, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 0.7% by mass or more, It may be 0.72% by mass or more, 0.75% by mass or more, 0.8% by mass or more, 1% by mass or more, 2% by mass or more, or 3% by mass or more. From these viewpoints, the content of the filler is 0 to 10% by mass, more than 0% by mass and 10% by mass or less, more than 0% by mass and 4% by mass or less, more than 0% by mass and 1% by mass or less, or. It may be more than 0% by mass and 0.8% by mass or less. From the same viewpoint, the content of carbon black may be in each of the above ranges with respect to the total mass of the effervescent composition.

The effervescent composition according to this embodiment can contain a plasticizer. Examples of the plasticizer include sebacic acid-based plasticizer, phthalate-based plasticizer, adipic acid-based plasticizer (dioctyl adipate (DOA), etc.), ester-based plasticizer, ether-ester-based plasticizer, thioether-based plasticizer, and aroma-based plasticizer. Examples include oils, naphthenic oils, and vegetable oils (rapeseed oils, etc.). Examples of the sebacic acid-based plasticizer include dioctyl sebacic acid (for example, bis (2-ethylhexyl) sebacate (DOS)), dimethyl sebacic acid, diethyl sebacic acid, dibutyl sebacic acid, diisopropyl sebacic acid, and sebacic acid derivatives such as dicapryl sebacic acid. Can be mentioned. The plasticizer may contain a sebacic acid-based plasticizer, may contain a sebacic acid derivative, and may contain bis (2-ethylhexyl) from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having a suitable softness. ) May include sebacate.

The content of the plasticizer may be in the following range with respect to 100 parts by mass of the chloroprene polymer from the viewpoint of obtaining a high foaming ratio and easily obtaining a foam having suitable softness. The content of the plasticizer is 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, 6 parts by mass or more, 8 parts by mass or more, 10 parts by mass or more, 12 parts by mass or more, 15 parts by mass or more, 18 parts by mass. The above, or 20 parts by mass or more may be used. The content of the plasticizer is 50 parts by mass or less, 48 parts by mass or less, 40 parts by mass or less, 35 parts by mass or less, 30 parts by mass or less, 28 parts by mass or less, 25 parts by mass or less, 22 parts by mass or less, 20 parts by mass. Hereinafter, it may be 18 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, 10 parts by mass or less, 8 parts by mass or less, 6 parts by mass or less, 5 parts by mass or less, or 3 parts by mass or less. From these viewpoints, the content of the plasticizer is 1 to 50 parts by mass, 1 to 30 parts by mass, 3 to 50 parts by mass, 3 to 30 parts by mass, 3 to 25 parts by mass, 5 to 25 parts by mass, 10 to 25 parts by mass, 10 to 20 parts by mass, 10 to 15 parts by mass, 3 to 20 parts by mass, 3 to 10 parts by mass, 5 to 20 parts by mass, 5 to 10 parts by mass, or 15 to 30 parts by mass. good. From the same viewpoint, the content of the sebacic acid derivative may be in each of the above ranges with respect to 100 parts by mass of the chloroprene polymer.

The content of the plasticizer may be in the following range based on the total mass of the effervescent composition from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having suitable softness. The content of the plasticizer is 1% by mass or more, 2% by mass or more, 3% by mass or more, 4% by mass or more, 5% by mass or more, 6% by mass or more, 7% by mass or more, 7.5% by mass or more, 8 It may be 10% by mass or more, 12% by mass or more, or 13% by mass or more. The content of the plasticizer is 30% by mass or less, 25% by mass or less, 20% by mass or less, 18% by mass or less, 16% by mass or less, 15% by mass or less, 14% by mass or less, 13% by mass or less, 12% by mass. Hereinafter, it may be 10% by mass or less, 8% by mass or less, 7.5% by mass or less, 7% by mass or less, 6% by mass or less, 5% by mass or less, 4% by mass or less, or 3% by mass or less. From these viewpoints, the content of the plasticizer is 1 to 30% by mass, 2 to 30% by mass, 2 to 20% by mass, 3 to 20% by mass, 3 to 10% by mass, 5 to 20% by mass, 5 to It may be 15% by mass or 5 to 10% by mass. From the same viewpoint, the content of the sebacic acid derivative may be in each of the above ranges with respect to the total mass of the effervescent composition.

The effervescent composition according to this embodiment can contain a foaming agent. Examples of the foaming agent include organic foaming agents and inorganic foaming agents (sodium hydrogen carbonate, ammonium carbonate, etc.). The foaming agent may contain an organic foaming agent from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having a suitable softness.

Examples of the organic foaming agent include a hydrazide foaming agent, a nitroso foaming agent, an azo foaming agent, and the like. The organic foaming agent may contain a hydrazide foaming agent from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having suitable softness.

Examples of the hydrazide-based foaming agent include p, p'-oxybisbenzenesulfonyl hydrazide, benzenesulfonyl hydrazide, toluenesulfonylhydrazide, hydrazodicarboxylic amide and the like. Examples of the nitroso-based foaming agent include N, N'-dinitrosopentamethylenetetramine. Examples of the azo-based foaming agent include diazoaminebenzene, azodicarbonamide, azobisisobutyronitrile, barium azodicarboxylate and the like.

The content of the foaming agent may be in the following range with respect to 100 parts by mass of the chloroprene polymer from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having suitable softness. The content of the foaming agent is 5 parts by mass or more, 6 parts by mass or more, 8 parts by mass or more, 10 parts by mass or more, 12 parts by mass or more, 15 parts by mass or more, 18 parts by mass or more, or 20 parts by mass or more. It's okay. The content of the foaming agent is 30 parts by mass or less, 25 parts by mass or less, 20 parts by mass or less, 18 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, 10 parts by mass or less, 8 parts by mass or less, 6 parts by mass. It may be less than or equal to 5 parts by mass or less. From these viewpoints, the content of the foaming agent is 5 to 30 parts by mass, 5 to 25 parts by mass, 5 to 20 parts by mass, 5 to 15 parts by mass, 5 to 10 parts by mass, 10 to 25 parts by mass, 10 to It may be 20 parts by mass or 10 to 15 parts by mass. From the same viewpoint, the content of the organic foaming agent may be in each of the above ranges and the content of the hydrazide foaming agent may be in the above ranges with respect to 100 parts by mass of the chloroprene polymer.

The content of the foaming agent may be in the following range based on the total mass of the foamable composition from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having suitable softness. The content of the foaming agent is 1% by mass or more, 2% by mass or more, 3% by mass or more, 4% by mass or more, 5% by mass or more, 6% by mass or more, 7% by mass or more, 7.5% by mass or more, 8 It may be 10% by mass or more, 12% by mass or more, or 13% by mass or more. The content of the foaming agent is 20% by mass or less, 15% by mass or less, 13% by mass or less, 12% by mass or less, 10% by mass or less, 8% by mass or less, 7.5% by mass or less, 7% by mass or less, 6 It may be 5% by mass or less, or 4% by mass or less. From these viewpoints, the content of the foaming agent is 1 to 20% by mass, 3 to 20% by mass, 3 to 15% by mass, 3 to 10% by mass, 5 to 15% by mass, 5 to 10% by mass, 6 to 6 to. It may be 10% by mass or 6 to 8% by mass. From the same viewpoint, the content of the organic foaming agent may be in each of the above ranges and the content of the hydrazide foaming agent may be in each of the above ranges based on the total mass of the effervescent composition.

The effervescent composition according to the present embodiment can contain a deliquescent agent. The deliquescent agent may have an action of cleaving the molecular chain of the polymer component, and may further have an action as a vulcanization accelerator. Examples of the antispasmodic agent include dithiocarbamate-based compounds such as pentamethylene dithiocarbamate piperidin salt (PPD), zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, and sodium dibutyldithiocarbamate; Compounds; 2,2'-dibenzamide diphenyl disulfide-based compounds; thiazole-based compounds; xanthogenic acid-based compounds; imidazole-based compounds and the like can be mentioned. The deliquescent agent may contain a dithiocarbamate-based compound from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having suitable softness.

The content of the deliquescent agent may be in the following range with respect to 100 parts by mass of the chloroprene polymer from the viewpoint of obtaining a high foaming ratio and easily obtaining a foam having suitable softness. The content of the deliquescent agent is 0.01 part by mass or more, 0.05 part by mass or more, 0.1 part by mass or more, 0.2 part by mass or more, 0.3 part by mass or more, 0.5 part by mass or more, 0.8 parts by mass or more, 1 part by mass or more, 1.2 parts by mass or more, 1.5 parts by mass or more, 1.8 parts by mass or more, 2 parts by mass or more, 2.5 parts by mass or more, or 3 parts by mass That may be the above. The content of the deliquescent agent is 10 parts by mass or less, 8 parts by mass or less, 5 parts by mass or less, 3 parts by mass or less, 2.5 parts by mass or less, 2 parts by mass or less, 1.8 parts by mass or less, 1.5 parts. By mass or less, 1.2 parts by mass or less, 1 part by mass or less, 0.8 parts by mass or less, 0.5 parts by mass or less, 0.3 parts by mass or less, 0.2 parts by mass or less, or 0.1 mass It may be less than or equal to a part. From these viewpoints, the content of the deliquescent agent is 0.01 to 10 parts by mass, 0.1 to 10 parts by mass, 0.1 to 3 parts by mass, 0.1 to 2 parts by mass, and 0.1 to 1 part. Parts by mass, 0.2 to 3 parts by mass, 0.2 to 2 parts by mass, 0.2 to 1 part by mass, 0.5 to 3 parts by mass, 1 to 3 parts by mass, 0.5 to 2 parts by mass, 0 It may be 5 to 1 part by mass or 1 to 2 parts by mass. From the same viewpoint, the content of the dithiocarbamate-based compound may be in each of the above ranges with respect to 100 parts by mass of the chloroprene polymer.

The content of the deliquescent agent may be in the following range based on the total mass of the effervescent composition from the viewpoint of obtaining a high foaming ratio and easily obtaining a foam having a suitable softness. The content of the antispasmodic agent is 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, 0.07% by mass or more, 0.1% by mass or more, 0.3% by mass or more, 0.4% by mass or more, 0.5% by mass or more, 0.7% by mass or more, 1% by mass or more, 1.2% by mass or more, 1.5% by mass or more, 1.8% by mass or more, or 2 It may be mass% or more. The content of the antispasmodic agent is 5% by mass or less, 4% by mass or less, 3% by mass or less, 2.5% by mass or less, 2% by mass or less, 1.8% by mass or less, 1.5% by mass or less, 1 .2% by mass or less, 1% by mass or less, 0.7% by mass or less, 0.5% by mass or less, 0.4% by mass or less, 0.3% by mass or less, 0.1% by mass or less, or 0. It may be 07% by mass or less. From these viewpoints, the content of the antispasmodic agent is 0.01 to 5% by mass, 0.05 to 5% by mass, 0.05 to 3% by mass, 0.1 to 3% by mass, and 0.1 to 2 by mass. .5% by mass, 0.1 to 2% by mass, 0.1 to 1.5% by mass, 0.1 to 1% by mass, 0.4 to 3% by mass, 0.5 to 3% by mass, 0.4 It may be up to 2% by mass, 0.4 to 1% by mass, 0.5 to 1% by mass, or 0.6 to 0.8% by mass. From the same viewpoint, the content of the dithiocarbamate-based compound may be in each of the above ranges with respect to the total mass of the effervescent composition.

The effervescent composition according to this embodiment may contain a vulcanizing agent. Examples of the sulfide agent include inorganic compounds such as sulfur, zinc oxide (ZnO), magnesium oxide (MgO), lead oxide, trilead tetroxide, iron trioxide, titanium dioxide, calcium oxide, and hydrotalcite. The vulcanizing agent may contain at least one selected from the group consisting of zinc oxide and magnesium oxide from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having suitable softness.

The content of the vulcanizing agent may be in the following range with respect to 100 parts by mass of the chloroprene polymer from the viewpoint of obtaining a high foaming ratio and easily obtaining a foam having suitable softness. The content of the sulfide may exceed 0 parts by mass, and is 0.1 parts by mass or more, 0.5 parts by mass or more, 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, and 4 parts by mass or more. It may be 5 parts by mass or more, 6 parts by mass or more, 7 parts by mass or more, 8 parts by mass or more, or 9 parts by mass or more. The content of the vulcanizing agent may be 20 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, 10 parts by mass or less, or 9 parts by mass or less. From these viewpoints, the content of the vulcanizing agent may be more than 0 parts by mass and 20 parts by mass or less, more than 0 parts by mass and 10 parts by mass or less, or 5 to 10 parts by mass.

The content of the vulcanizing agent may be in the following range based on the total mass of the effervescent composition from the viewpoint of obtaining a high foaming ratio and easily obtaining a foam having suitable softness. The content of the sulfide may exceed 0% by mass, 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 2% by mass or more, 3% by mass or more, 4% by mass or more, It may be 5% by mass or more, 6% by mass or more, or 7% by mass or more. The content of the vulcanizing agent may be 20% by mass or less, 15% by mass or less, 10% by mass or less, 8% by mass or less, or 7% by mass or less. From these viewpoints, the content of the vulcanizing agent may be more than 0% by mass and 20% by mass or less, more than 0% by mass and 10% by mass or less, or 3 to 8% by mass.

The effervescent composition according to this embodiment may contain a vulcanization accelerator. Examples of the vulcanization accelerator include thiourea compounds such as ethylene thiourea, diethyl thiourea, trimethyl thiourea, triethyl thiourea, N, N'-diphenyl thiourea and N, N'-diethyl thiourea; and guanidine compounds such as 1,3-diphenyl guanidine. Examples include compounds. The vulcanization accelerator may contain at least one selected from the group consisting of ethylenethiourea and guanidine from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having suitable softness.

In the effervescent composition according to the present embodiment, as components other than the above-mentioned components, a resin component (excluding chloroprene polymer), a rubber component (excluding chloroprene polymer), a lubricant, an antiaging agent, a surfactant, and an emulsifying agent. Additives such as stabilizers, viscosity modifiers, anti-aging agents, preservatives and the like can be contained. The effervescent composition according to this embodiment does not have to contain an organic peroxide. The content of the organic peroxide may be less than 1 part by mass or 0.1 part by mass or less with respect to 100 parts by mass of the chloroprene polymer. The effervescent composition according to this embodiment does not have to contain chlorinated paraffin. The content of chlorinated paraffin may be less than 5 parts by mass or 1 part by mass or less with respect to 100 parts by mass of the chloroprene polymer.

The effervescent composition according to this embodiment may contain a thermoplastic resin as a resin component. Examples of the thermoplastic resin include terpene-based resin, rosin-based resin, styrene-based resin, kumaron resin, xylene resin and the like. The thermoplastic resin may contain a terpene resin from the viewpoint that a foam having suitable adhesiveness can be easily obtained, a high foaming ratio can be easily obtained, and a foam having suitable softness can be easily obtained. Examples of the terpene-based resin include terpene resin, aromatic-modified terpene resin, terpene phenol resin, hydrogenated terpene phenol resin, hydrogenated terpene resin, and hydrogenated aromatic-modified terpene resin. The thermoplastic resin may contain a liquid resin at 120 ° C. or lower from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having suitable softness.

The softening point of the thermoplastic resin (for example, a terpene resin) may be in the following range from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having a suitable softness. The softening point may be 20 ° C., 25 ° C. or higher, 30 ° C. or higher, 40 ° C. or higher, 50 ° C. or higher, 60 ° C. or higher, 70 ° C. or higher, 80 ° C. or higher, or 85 ° C. or higher. The softening point may be 150 ° C. or lower, 120 ° C. or lower, 100 ° C. or lower, 90 ° C. or lower, or 85 ° C. or lower. From these viewpoints, the softening point may be 20 to 150 ° C, 50 to 150 ° C, 60 to 120 ° C, or 80 to 100 ° C.

The content of the thermoplastic resin may be in the following range with respect to 100 parts by mass of the chloroprene polymer from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having suitable softness. The content of the thermoplastic resin is 0.1 part by mass or more, 0.5 part by mass or more, 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, 8 parts by mass or more, or 10 parts by mass or more. It's okay. The content of the thermoplastic resin may be 100 parts by mass or less, 80 parts by mass or less, 50 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less. From these viewpoints, the content of the thermoplastic resin may be 0.1 to 100 parts by mass, 1 to 50 parts by mass, or 5 to 20 parts by mass.

The content of the thermoplastic resin may be in the following range based on the total mass of the effervescent composition from the viewpoint of obtaining a high foaming ratio and easily obtaining a foam having suitable softness. The content of the thermoplastic resin may exceed 0% by mass, and may be 1% by mass or more, 3% by mass or more, 5% by mass or more, 6% by mass or more, or 7% by mass or more. The content of the thermoplastic resin may be 20% by mass or less, 15% by mass or less, 12% by mass or less, 10% by mass or less, or 8% by mass or less. From these viewpoints, the content of the thermoplastic resin may be more than 0% by mass and 20% by mass or less.

The content of the terpene resin is 50% by mass or more and 70% by mass or more based on the total mass of the thermoplastic resin from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having suitable softness. , 90% by mass or more, 95% by mass or more, 98% by mass or more, or 99% by mass or more. The thermoplastic resin may be an embodiment made of a terpene-based resin (a mode in which substantially 100% by mass of the thermoplastic resin is a terpene-based resin).

As the resin component, ethylene, α-olefin, non-conjugated polyene copolymer, poly (alkylphenol) polysulfide, or the like may be used. The content of the ethylene / α-olefin / non-conjugated polyene copolymer may be less than 3 parts by mass or 1 part by mass or less with respect to 100 parts by mass of the chloroprene polymer. The content of the poly (alkylphenol) polysulfide may be less than 1 part by mass or 0.1 part by mass or less with respect to 100 parts by mass of the chloroprene polymer. The effervescent composition according to this embodiment does not have to contain a water-absorbent resin as a resin component. The content of the water-absorbent resin may be less than 10 parts by mass or 1 part by mass or less with respect to 100 parts by mass of the chloroprene polymer.

The content of the resin component may be in the following range with respect to 100 parts by mass of the chloroprene polymer from the viewpoint of easily obtaining a high foaming ratio and easily obtaining a foam having suitable softness. The content of the resin component is 0.1 part by mass or more, 0.5 part by mass or more, 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, 8 parts by mass or more, or 10 parts by mass or more. good. The content of the resin component may be 100 parts by mass or less, 80 parts by mass or less, 50 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less. From these viewpoints, the content of the resin component may be 0.1 to 100 parts by mass, 1 to 50 parts by mass, or 5 to 20 parts by mass.

The rubber components include natural rubber, isoprene rubber, butyl rubber, nitrile rubber, hydride nitrile rubber, butadiene rubber, styrene-butadiene rubber, ethylene-propylene-diene rubber, chloroprene rubber and other diene rubbers; butyl rubber, ethylene-propylene rubber and the like. Non-diene rubber and the like can be mentioned. The rubber component may contain butyl rubber from the viewpoint of improving the adhesiveness to the metal plate to which the oil is attached.

The content of the rubber component may be in the following range with respect to 100 parts by mass of the chloroprene polymer from the viewpoint of improving the adhesiveness and easily obtaining a high foaming ratio. The content of the rubber component is 0.1 part by mass or more, 0.5 part by mass or more, 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, 8 parts by mass or more, or 10 parts by mass or more. good. The content of the rubber component may be 100 parts by mass or less, 80 parts by mass or less, 50 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less. From these viewpoints, the content of the rubber component may be 0.1 to 100 parts by mass, 1 to 50 parts by mass, or 5 to 20 parts by mass.

By using a lubricant, when the effervescent composition is kneaded, the effervescent composition can be easily peeled off from the roll, the molding die, the screw of the extruder, or the like. Examples of the lubricant include fatty acids such as stearic acid; paraffin-based processing aids such as paraffin wax; and fatty acid amides. The content of the lubricant may be 0.5 to 5 parts by mass with respect to 100 parts by mass of the chloroprene polymer.

Examples of the anti-aging agent include amine-based anti-aging agents, imidazole-based anti-aging agents, carbamic acid metal salts, phenol-based anti-aging agents, and ozone-based anti-aging agents (for example, N-phenyl-N'-(1,3-dimethylbutyl)). ) -P-Phenylenediamine) and the like. Examples of the amine-based antiaging agent include octylated diphenylamine, 4,4'-bis (α, α-dimethylbenzyl) diphenylamine and the like. The content of the antioxidant may be 1 to 10 parts by mass with respect to 100 parts by mass of the chloroprene polymer.

The effervescent composition according to this embodiment can be obtained by kneading the above-mentioned components. As the kneading device, a mixer, a Banbury mixer, a kneader mixer, a double roll or the like can be used.

The foam according to the present embodiment may have open cells in which hollow cells are connected to each other. The open cell contains a plurality of hollow cells. By "open cell" is meant a structure in which at least a portion of the cells formed in the foam is continuous. The foam may have an open cell structure or a semi-continuous semi-closed cell structure. The open cell structure refers to a structure in which the open cell ratio is 100%. In the semi-continuous semi-closed cell structure, the lower limit of the open cell ratio exceeds 0% and may be 10% or more. In the semi-continuous semi-closed cell structure, the upper limit of the open cell ratio is less than 100% and may be less than 98%.

The foam according to this embodiment may be a single layer. The foam according to the present embodiment can have physical properties suitable for various uses in a single layer state. The foam according to the present embodiment can be suitably used in buildings, automobiles, railroad vehicles, aircraft, electrical equipment, audio equipment, acoustic facilities, etc., and members (insulation materials, impacts) used for these applications. Absorbent material, vibration-proof material, sound-absorbing material, etc.) can be configured.

The method for producing a foam according to the present embodiment includes a foaming step for foaming the foamable composition according to the present embodiment. In the foaming step, the effervescent composition can be heated and foamed. The temperature of the heated foaming may be, for example, 100 to 220 ° C, 120 to 200 ° C, or 130 to 160 ° C.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to these Examples.

<Making foam>
(Examples 1 to 10 and Comparative Examples 1 to 4)
Chloroprene polymer (sulfur-modified, manufactured by Denka Co., Ltd., trade name: Denkachloroprene PM-40, manufactured by Nippon Roll Manufacturing Co., Ltd., roll temperature: 40 ° C.) using an 8-inch roll, the above-mentioned general formula ( 100 parts by mass of polymer without structure represented by I), filler (carbon black (HAF), manufactured by Asahi Carbon Co., Ltd., trade name: Asahi # 70), plasticizer (bis (2-ethylhexyl)) Sevacate (DOS), manufactured by Shin Nihon Rika Co., Ltd., trade name: Sunsocizer DOS, foaming agent (p, p'-oxybisbenzenesulfonyl hydrazide (OBSH), manufactured by Sankyo Kasei Co., Ltd., trade name: Cellmic S) , Shaking agent (pentamethylene dithiocarbamate piperidin salt (PPD), manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., trade name: Noxeller PPD), stearic acid (lubricant, manufactured by Kao Co., Ltd., trade name: Lunac S-70V) 1 By weight, paraffin wax (lubricant, manufactured by Nippon Seikan Co., Ltd., trade name: Paraffin Wax-135), 3 parts by mass, octylated diphenylamine (antiaging agent, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., trade name: Nocrack AD- F) 1 part by mass, magnesium oxide (sulfurizing agent, MgO, manufactured by Kyowa Chemical Industry Co., Ltd., trade name: Kyowamag 150) 4 parts by mass, and zinc oxide (sulfurizing agent, ZnO, manufactured by Sakai Chemical Industry Co., Ltd.) A foamable composition (compound) was obtained by kneading 5 parts by mass of (trade name: 2 types of zinc oxide) in accordance with JIS K 6299. Table 1 shows the blending amounts of the chloroprene polymer, the filler, the plasticizer, the foaming agent and the deliquescent agent in each Example and each Comparative Example.

(Example 11)
Effervescent composition by carrying out in the same manner as in Example 1 except that 10 parts by mass of a thermoplastic resin (aromatically modified terpene resin, manufactured by Yasuhara Chemical Co., Ltd., trade name: YS resin TO85, softening point: 85 ° C.) was further used. I got a thing (compound).

<Maximum torque X and Mooney viscosity Y>
The maximum torque value X and Mooney viscosity Y were measured by the following procedure. Table 1 shows the results of these measurements, the value A (= 1.33X + 30.67) corresponding to the right side of the above formula (A), and the magnitude relationship between the Mooney viscosity Y and the value A. Further, FIG. 1 shows the relationship between the maximum torque value X and the Mooney viscosity Y.

(Maximum torque value X)
The vulcanization curve of the effervescent composition was measured using a rheometer (manufactured by EKTRON, trade name: EKT-2000SP) at 150 ° C. for 20 minutes in accordance with ISO 6502 / ASTM D5289. The maximum value X of the torque (vulcanization torque) in this vulcanization curve was obtained. Preliminary test A preliminary test was conducted at 80 ° C. for 3 minutes using 7 g of the sample, and the mass of the hollow part of the die composed of the upper and lower dies was measured for the sample after the preliminary test, and 70% of the mass was the sample of the main test. It was adopted as the filling amount.

(Moony viscosity Y)
Measured with an L-type rotor at a test temperature of 100 ° C and a preheating time of 1 minute using a Mooney viscosity tester (manufactured by Shimadzu Corporation, trade name: SMV-301) in accordance with Japanese Industrial Standards JIS K 630-1. The Mooney viscosity Y (ML _{1 + 4} ) of the above-mentioned effervescent composition was measured under the test conditions of 4 minutes.

<Evaluation>
Using the above-mentioned effervescent composition, the effervescence ratio and the hardness of the foam were evaluated. The results are shown in Table 1.

(Effervescence magnification)
Using the above-mentioned effervescent composition, a sheet having a thickness of 3 mm was prepared by an open roll. A test sample having a length of 20 mm, a width of 20 mm, and a thickness of 3 mm was cut out from this sheet. A foam was obtained by placing a test sample on a release sheet and placing it in a gear oven at 150 ° C. for 20 minutes to foam it. After removing the foam from the gear oven and holding it at 25 ° C. for 30 minutes, the dimensions (length, width and thickness) of the foam were measured with a caliper. The foaming ratio [unit:%] was calculated from the following formula based on the volume change before and after foaming. A foaming ratio of 600% or more was judged to be good.
Foaming magnification = [(Volume after foaming-Volume before foaming) / Volume before foaming] x 100

(hardness)
A foam was obtained in the same manner as in the evaluation of the foaming ratio described above. Using a rubber hardness tester (manufactured by Polymer Meter Co., Ltd., trade name: Asker rubber hardness tester F type), a disk-shaped pressure surface was gently placed on the foam. The value was read by using the own weight of the hardness tester as the measured pressure, and the hardness of the foam (25 ° C.) was obtained.

Claims

An effervescent composition containing a chloroprene polymer.
The maximum value X (unit: dN · m) of torque in the vulcanization curve of the effervescent composition measured at 150 ° C., and the effervescent composition measured at 100 ° C. with a preheating time of 1 minute and a measurement time of 4 minutes. An effervescent composition in which the Mooney viscosity Y of the product satisfies the following formula (A).
Y ≤ -1.33X + 30.67 ... (A)
The effervescent composition according to claim 1, wherein the maximum value X of the torque is 20.0 dN · m or less.
The effervescent composition according to claim 1 or 2, wherein the Mooney viscosity Y is 15 or less.
The effervescent composition according to any one of claims 1 to 3, wherein the chloroprene polymer contains a sulfur-modified chloroprene polymer.
The effervescent composition according to any one of claims 1 to 4, further containing a thermoplastic resin.
The effervescent composition according to claim 5, wherein the thermoplastic resin contains a terpene-based resin.
The foam of the effervescent composition according to any one of claims 1 to 6.