JP2023170763A - Foaming rate improver for polymer material, foamer composition for polymer material, polymer composition, and foam - Google Patents

Abstract

To provide a foamer that improves the foaming ratio during foam production.SOLUTION: A foaming rate improver for polymer material contains (a) a pyrazolone compound and (b) a salt.SELECTED DRAWING: None

Description

The present invention relates to a foaming ratio improver for polymeric materials, a foaming agent composition for polymeric materials, a polymeric composition, and a foam.

Currently, polymer compositions, which are petrochemical products, are used in automobile parts, building materials, industrial parts, infrastructure parts, and the like. There is a desire to lower the specific gravity of a polymer composition or to provide a polymer composition with a heat insulating performance by including voids therein. In order to meet these demands, foaming techniques have conventionally been employed, and among these techniques, a technique in which a polymeric material is foamed using a chemical foaming agent has been adopted. However, in consideration of environmental issues and the like, there is a need to reduce _CO2 emissions, and there is an even greater need to reduce the amount of chemical blowing agents used.

Patent Document 1 is a technology provided by the present applicant, in which the foam layer contains at least one compound selected from a hydrazide compound, an azole compound, or an azine compound in an automobile ceiling material comprising a foam layer. Discloses an automotive ceiling material containing.

Patent Document 2 discloses a rubber composition in which at least one rubber component selected from natural rubber and synthetic rubber is blended with a foaming agent and a foaming aid containing at least one selected from hydrazide compounds and hydrazone compounds. is disclosed.

Japanese Patent Application Publication No. 2000-6730 Japanese Patent Application Publication No. 2004-161898

An object of the present invention is to provide a foaming agent that imparts high expansion ratio during foam production.

When foaming a mixture in which a pyrazolone compound such as 3-methyl-5-pyrazolone and an inorganic foaming agent such as baking soda are stored in the coexistence, the expansion ratio and foam cell refinement are Further improvement is required.

In a blowing agent composition that uses a chemical blowing agent such as baking soda, the present inventor has discovered that by using a pyrazolone compound such as 3-methyl-5-pyrazolone and a salt such as calcium carbonate, the blowing agent composition can be maintained for a long period of time. The inventors have found that the deterioration of the blowing agent composition can be suppressed during storage, and the foam exhibits an excellent expansion ratio and fine foam cells.

Based on this knowledge, the present inventor conducted further research and completed the present invention.

The present invention provides the following foaming ratio improver for polymeric materials, foaming agent composition for polymeric materials, polymeric compositions, and foams.

Item 1.
(a) At least one compound selected from compounds represented by formulas (1) and (2), and salts of the compounds:

（式（１）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は同一又は異なって、水素原子、アルキル基、アラルキル基、アリール基、又は複素環基を示す。Ｒ^３とＲ^４とは互いに結合してアルキリデン基を形成してもよく、Ｒ^２、Ｒ^３及びＲ^４のいずれか２つが互いに結合してアルキレン基を形成してもよい。これら各基は、それぞれ１個以上の置換基を有していてもよい。）

(In formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group. What are R ³ and R ⁴ ? They may be combined with each other to form an alkylidene group, or any two of R ² , R ³ and R ⁴ may be combined with each other to form an alkylene group. Each of these groups has one or more substituents. (It may have a group.)

（式（２）中、Ｒ^５、Ｒ^７及びＲ^８は同一又は異なって、水素原子、アミノ基、アルキル基、アラルキル基、アリール基、又は複素環基を示し、Ｒ^６はアルキル基、アラルキル基、アリール基、又は複素環基を示す。これら各基は、それぞれ１個以上の置換基を有していてもよい。）
及び
（ｂ）塩類
を含む、高分子材料用発泡倍率向上剤。

(In formula (2), R ⁵ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, an amino group, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and R ⁶ is an alkyl group, an aralkyl group. group, aryl group, or heterocyclic group. Each of these groups may have one or more substituents.)
and (b) a foaming ratio improver for polymeric materials containing salts.

Item 2.
A foaming agent composition for a polymeric material, comprising the foaming ratio improver for a polymeric material according to item 1 above, and (c) a chemical foaming agent.

Item 3.
(a) At least one compound selected from compounds represented by formulas (1) and (2), and salts of the compounds:

（式（１）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は同一又は異なって、水素原子、アルキル基、アラルキル基、アリール基、又は複素環基を示す。Ｒ^３とＲ^４とは互いに結合してアルキリデン基を形成してもよく、Ｒ^２、Ｒ^３及びＲ^４のいずれか２つが互いに結合してアルキレン基を形成してもよい。これら各基は、それぞれ１個以上の置換基を有していてもよい。）

(In formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group. What are R ³ and R ⁴ ? They may be combined with each other to form an alkylidene group, or any two of R ² , R ³ and R ⁴ may be combined with each other to form an alkylene group. Each of these groups has one or more substituents. (It may have a group.)

（式（２）中、Ｒ^５、Ｒ^７及びＲ^８は同一又は異なって、水素原子、アミノ基、アルキル基、アラルキル基、アリール基、又は複素環基を示し、Ｒ^６はアルキル基、アラルキル基、アリール基、又は複素環基を示す。これら各基は、それぞれ１個以上の置換基を有していてもよい。）
（ｂ）塩類、及び
（ｃ）化学発泡剤
を含む、高分子材料用発泡剤組成物。

(In formula (2), R ⁵ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, an amino group, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and R ⁶ is an alkyl group, an aralkyl group. group, aryl group, or heterocyclic group. Each of these groups may have one or more substituents.)
(b) a salt; and (c) a blowing agent composition for a polymeric material, comprising a chemical blowing agent.

Item 4.
A blowing agent composition for a polymeric material according to item 2 or 3 above, and (d) a polymeric material.
A polymer composition containing.

Item 5.
(a) At least one compound selected from compounds represented by formulas (1) and (2), and salts of the compounds:

（式（１）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は同一又は異なって、水素原子、アルキル基、アラルキル基、アリール基、又は複素環基を示す。Ｒ^３とＲ^４とは互いに結合してアルキリデン基を形成してもよく、Ｒ^２、Ｒ^３及びＲ^４のいずれか２つが互いに結合してアルキレン基を形成してもよい。これら各基は、それぞれ１個以上の置換基を有していてもよい。）

(In formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group. What are R ³ and R ⁴ ? They may be combined with each other to form an alkylidene group, or any two of R ² , R ³ and R ⁴ may be combined with each other to form an alkylene group. Each of these groups has one or more substituents. (It may have a group.)

（式（２）中、Ｒ^５、Ｒ^７及びＲ^８は同一又は異なって、水素原子、アミノ基、アルキル基、アラルキル基、アリール基、又は複素環基を示し、Ｒ^６はアルキル基、アラルキル基、アリール基、又は複素環基を示す。これら各基は、それぞれ１個以上の置換基を有していてもよい。）
（ｂ）塩類
（ｃ）化学発泡剤、及び
（ｄ）高分子材料
を含む、高分子組成物。

(In formula (2), R ⁵ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, an amino group, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and R ⁶ is an alkyl group, an aralkyl group. group, aryl group, or heterocyclic group. Each of these groups may have one or more substituents.)
(b) a salt; (c) a chemical blowing agent; and (d) a polymeric composition comprising a polymeric material.

Item 6.
A foam obtained by foaming the polymer composition according to item 4 or 5 above.

By combining the foaming ratio improver for polymeric materials of the present invention with a chemical foaming agent, it is possible to improve the foaming ratio in a foam containing a rubber component, etc., and to make the cells finer.

The present invention can provide a foaming agent that imparts high expansion ratio during foam production.

The present invention will be explained in detail below.

As used herein, "comprise" and "containing" include "comprise," "consist essentially of," and "consist of." It is a concept.

In this specification, when a numerical range is indicated as "A to B", the numerical range means A or more and B or less.

[1] Foaming ratio improver for polymeric materials The foaming ratio improver for polymeric materials of the present invention is:
(a) At least one compound selected from compounds represented by formulas (1) and (2), and salts of the compounds:

（式（１）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は同一又は異なって、水素原子、アルキル基、アラルキル基、アリール基、又は複素環基を示す。Ｒ^３とＲ^４とは互いに結合してアルキリデン基を形成してもよく、Ｒ^２、Ｒ^３及びＲ^４のいずれか２つが互いに結合してアルキレン基を形成してもよい。これら各基は、それぞれ１個以上の置換基を有していてもよい。）

(In formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group. What are R ³ and R ⁴ ? They may be combined with each other to form an alkylidene group, or any two of R ² , R ³ and R ⁴ may be combined with each other to form an alkylene group. Each of these groups has one or more substituents. (It may have a group.)

（式（２）中、Ｒ^５、Ｒ^７及びＲ^８は同一又は異なって、水素原子、アミノ基、アルキル基、アラルキル基、アリール基、又は複素環基を示し、Ｒ^６はアルキル基、アラルキル基、アリール基、又は複素環基を示す。これら各基は、それぞれ１個以上の置換基を有していてもよい。）
及び
（ｂ）塩類を含む。

(In formula (2), R ⁵ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, an amino group, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and R ⁶ is an alkyl group, an aralkyl group. group, aryl group, or heterocyclic group. Each of these groups may have one or more substituents.)
and (b) contains salts.

The foaming ratio improver for polymeric materials of the present invention contains pyrazolone compounds such as 3-methyl-5-pyrazolone and salts such as calcium carbonate, and when using chemical foaming agents such as baking soda, polymeric materials are used. In the foamed material, the expansion ratio of the foamed material can be improved, and the cells of the foamed material can be made finer.

The foaming ratio improver for polymeric materials of the present invention contains a pyrazolone compound such as 3-methyl-5-pyrazolone and salts such as calcium carbonate, and when a chemical foaming agent such as baking soda is used, a chemical foaming agent is used. In the foaming agent composition for polymeric materials, deterioration of the composition (deterioration of foaming performance and discoloration) can be suppressed even if the composition is stored for a long period of time.

In the production of foams containing rubber components, kneading methods have diversified, and the timing of adding chemicals has been adjusted.

The foaming ratio improver for polymeric materials of the present invention contains salts such as calcium carbonate, and can maintain or improve foaming performance, making it compatible with diversified kneading methods.

The foaming ratio improver for polymeric materials of the present invention is produced by using pyrazolone compounds such as 3-methyl-5-pyrazolone and salts such as calcium carbonate when kneading polymeric materials such as rubber components. In foams containing polymeric materials such as rubber components and resins, the expansion ratio can be improved.

In the foaming ratio improver for polymeric materials of the present invention, a pyrazolone compound such as 3-methyl-5-pyrazolone forms a network between the polymeric materials (polymer components) used in the foam, resulting in crosslinking and vulcanization. It is thought that it acts on the system.

By combining the foaming ratio improver for polymeric materials of the present invention with a chemical foaming agent, it is possible to improve the foaming ratio in a foam containing a rubber component, etc., and to make the cells finer.

(a) At least one compound selected from compounds represented by formulas (1) and (2) and salts of the compounds
The compound represented by formula (1) and the salt component (a) of the compound are compounds represented by formula (1) below.

Hereinafter, the compound and its salt will be collectively referred to as simply compound (1).

式（１）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は同一又は異なって、水素原子、アルキル基、アラルキル基、アリール基、又は複素環基を示す。

In formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group.

In formula (1), R ³ and R ⁴ may be combined with each other to form an alkylidene group, or any two of R ² , R ³ and R ⁴ may be combined with each other to form an alkylene group. good.

In formula (1), each of these groups may have one or more substituents.

The compound represented by formula (2) and the salt component (a) of the compound are compounds represented by formula (2) below.

Hereinafter, the compound and its salt will be collectively referred to as simply compound (2).

式（２）中、Ｒ^５、Ｒ^７及びＲ^８は同一又は異なって、水素原子、アミノ基、アルキル基、アラルキル基、アリール基、又は複素環基を示し、Ｒ^６はアルキル基、アラルキル基、アリール基、又は複素環基を示す。

In formula (2), R ⁵ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, an amino group, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and R ⁶ is an alkyl group, an aralkyl group , an aryl group, or a heterocyclic group.

In formula (2), each of these groups may have one or more substituents.

In compound (1) or (2), the "alkyl group" is not particularly limited and includes, for example, a linear, branched or cyclic alkyl group, and specifically, for example, methyl, ethyl , straight or branched alkyl groups having 1 to 4 carbon atoms such as n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, furthermore 1-ethylpropyl, n-pentyl, Isopentyl, neopentyl, n-hexyl, isohexyl, 3-methylpentyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, 5-propylnonyl, n-tridecyl, n- Linear or branched alkyl groups with 5 to 18 carbon atoms including tetradecyl, n-pentadecyl, hexadecyl, heptadecyl, octadecyl, etc.; 3 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. -8 cyclic alkyl groups and the like.

In compound (1) or (2), the "aralkyl group" is not particularly limited and includes, for example, benzyl, phenethyl, trityl, 1-naphthylmethyl, 2-(1-naphthyl)ethyl, 2-(2-naphthyl). ) Ethyl group, etc.

In compound (1) or (2), the "aryl group" is not particularly limited and includes, for example, phenyl, biphenyl, naphthyl, dihydroindenyl, 9H-fluorenyl group, and the like.

In compound (1) or (2), the "heterocyclic group" is not particularly limited, and includes, for example, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrazinyl, 2-pyrimidyl, 4-pyrimidyl, 5 -pyrimidyl, 3-pyridazyl, 4-pyridazyl, 4-(1,2,3-triazyl), 5-(1,2,3-triazyl), 2-(1,3,5-triazyl), 3-( 1,2,4-triazyl), 5-(1,2,4-triazyl), 6-(1,2,4-triazyl), 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6 -Quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 2-quinoxalyl, 3-quinoxalyl, 5-quinoxalyl , 6-quinoxalyl, 7-quinoxalyl, 8-quinoxalyl, 3-cinnolyl, 4-cinnolyl, 5-cinnolyl, 6-cinnolyl, 7-cinnolyl, 8-cinnolyl, 2-quinazolyl, 4-quinazolyl, 5-quinazolyl, 6 -Quinazolyl, 7-quinazolyl, 8-quinazolyl, 1-phthaladyl, 4-phthaladyl, 5-phthaladyl, 6-phthaladyl, 7-phthaladyl, 8-phthaladyl, 1-tetrahydroquinolyl, 2-tetrahydroquinolyl, 3-tetrahydro Quinolyl, 4-tetrahydroquinolyl, 5-tetrahydroquinolyl, 6-tetrahydroquinolyl, 7-tetrahydroquinolyl, 8-tetrahydroquinolyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-furyl, 3 -Furyl, 2-thienyl, 3-thienyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl , 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 4-(1,2,3- thiadiazolyl), 5-(1,2,3-thiadiazolyl), 3-(1,2,5-thiadiazolyl), 2-(1,3,4-thiadiazolyl), 4-(1,2,3-oxadiazolyl) , 5-(1,2,3-oxadiazolyl), 3-(1,2,4-oxadiazolyl), 5-(1,2,4-oxadiazolyl), 3-(1,2,5-oxadiazolyl), 2 -(1,3,4-oxadiazolyl), 1-(1,2,3-triazolyl), 4-(1,2,3-triazolyl), 5-(1,2,3-triazolyl), 1-( 1,2,4-triazolyl), 3-(1,2,4-triazolyl), 5-(1,2,4-triazolyl), 1-tetrazolyl, 5-tetrazolyl, 1-indolyl, 2-indolyl, 3 -Indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl, 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl, 1-benzimidazolyl , 2-benzimidazolyl, 4-benzimidazolyl, 5-benzimidazolyl, 6-benzimidazolyl, 7-benzimidazolyl, 2-benzofuranyl, 3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl, 7-benzofuranyl, 1-isobenzofuranyl Nyl, 3-isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzofuranyl, 7-isobenzofuranyl, 2-benzothienyl, 3-benzothienyl, 4-benzothienyl, 5 -Benzothienyl, 6-benzothienyl, 7-benzothienyl, 2-benzoxazolyl, 4-benzoxazolyl, 5-benzoxazolyl, 6-benzoxazolyl, 7-benzoxazolyl, 2 -Benzothiazolyl, 4-benzothiazolyl, 5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl, 1-indazolyl, 3-indazolyl, 4-indazolyl, 5-indazolyl, 6-indazolyl, 7-indazolyl, 2-morpholyl, 3-morpholyl , 4-morpholyl, 1-piperazyl, 2-piperazyl, 1-piperidyl, 2-piperidyl, 3-piperidyl, 4-piperidyl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydro Thiopyranyl, 3-tetrahydrothiopyranyl, 4-tetrahydrothiopyranyl, 1-pyrrolidyl, 2-pyrrolidyl, 3-pyrrolidyl, furanyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydro Examples include thienyl, 5-methyl-3-oxo-2,3-dihydro-1H-pyrazol-4-yl group, and morpholino group.

In compound (1) or (2), the "alkylene group" is not particularly limited, and includes, for example, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, etc. having 2 carbon atoms. -7 alkylene groups may be mentioned. These alkylene groups may contain a nitrogen atom, an oxygen atom, a sulfur atom, or may have a phenylene group interposed therebetween. Examples of such _alkylene groups include -CH ₂ NHCH ₂ -, -CH _{2 NHCH 2} CH 2 -, -CH ₂ NHNHCH ₂ -, -CH ₂ CH 2 NHCH ₂ CH ₂ -, -CH ₂ NHNHCH ₂ CH ₂ -, -CH ₂ NHCH ₂ NHCH ₂ -, -CH ₂ CH 2 CH ₂ NHCH ₂ CH ₂ CH ₂ -, -CH ₂ OCH ₂ CH ₂ -, -CH ₂ CH ₂ OCH _{2 CH 2 -} , -CH ₂ SCH ₂ CH ₂ -, -CH ₂ CH ₂ SCH ₂ CH ₂ -,

等が挙げられる。

etc.

In compound (1) or (2), the "alkylidene group" has about 1 to 4 carbon atoms, is not particularly limited, and includes, for example, methylidene, ethylidene, propylidene, isopropylidene, butylidene groups, etc. .

These alkyl groups, aralkyl groups, aryl groups, heterocyclic groups, and alkylene groups may each have one or more substituents at any substitutable position.

The "substituent" is not particularly limited, and includes, for example, a halogen atom, an amino group, an aminoalkyl group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an amide group, a carboxyl group, a carboxyalkyl group, a formyl group, and a nitrile group. , nitro group, alkyl group, hydroxyalkyl group, hydroxyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, thiol group, alkylthio group, arylthio group, and the like.

The substituent may preferably have 1 to 5, more preferably 1 to 3 substituents.

In compound (1) or (2), the "halogen atom" includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferably a chlorine atom, a bromine atom, and an iodine atom.

In compound (1) or (2), the "amino group" includes not only the amino group represented by -NH ₂ but also, for example, methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino. , straight-chain or Branched monoalkylamino group having about 1 to 6 carbon atoms; dialkylamino having two linear or branched alkyl groups having about 1 to 2 carbon atoms such as dimethylamino, ethylmethylamino, and diethylamino groups Substituted amino groups such as groups are also included.

In compound (1) or (2), the "aminoalkyl group" is not particularly limited, and includes, for example, aminomethyl, methylaminomethyl, ethylaminomethyl, dimethylaminomethyl, ethylmethylaminomethyl, diethylaminomethyl, 2- Aminoethyl, 2-(methylamino)ethyl, 2-(ethylamino)ethyl, 2-(dimethylamino)ethyl, 2-(ethylmethylamino)ethyl, 2-(diethylamino)ethyl, 3-aminopropyl, 3- Aminoalkyl groups having about 1 to 7 carbon atoms such as (methylamino)propyl, 3-(ethylamino)propyl, 3-(dimethylamino)propyl, 3-(ethylmethylamino)propyl, 3-(diethylamino)propyl groups, etc. , a monoalkyl-substituted aminoalkyl group, a dialkyl-substituted aminoalkyl group, and the like.

In compound (1) or (2), the "alkoxycarbonyl group" is not particularly limited, and examples thereof include linear or branched alkoxycarbonyl groups having 1 to 4 carbon atoms such as methoxycarbonyl and ethoxycarbonyl groups. Can be mentioned.

In compound (1) or (2), the "acyl group" is not particularly limited, and examples thereof include linear or branched alkylcarbonyl groups having 1 to 4 carbon atoms such as acetyl, propionyl, and pivaloyl groups. It will be done.

In compound (1) or (2), the "acyloxy group" is not particularly limited, and examples thereof include linear or branched acyloxy groups having 1 to 4 carbon atoms such as acetyloxy, propionyloxy, and n-butyryloxy groups. Examples include groups.

In compound (1) or (2), the "amide group" is not particularly limited, and includes, for example, carboxylic acid amide groups such as acetamide and benzamide groups; thioamide groups such as thioacetamide and thiobenzamide groups; N-methylacetamide , N-substituted amide groups such as N-benzylacetamide groups; and the like.

In compound (1) or (2), the "carboxyalkyl group" is not particularly limited and includes, for example, carboxymethyl, carboxyethyl, carboxy-n-propyl, carboxy-n-butyl, carboxy-n-pentyl, carboxy Examples include carboxyalkyl groups such as -n-hexyl.

In compound (1) or (2), the "hydroxyalkyl group" is not particularly limited, and includes, for example, hydroxyalkyl groups such as hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, and hydroxy-n-butyl groups. It will be done.

In compound (1) or (2), the "alkoxy group" is not particularly limited and includes, for example, a linear, branched or cyclic alkoxy group, and specifically, for example, methoxy, ethoxy , n-propoxy, isopropoxy, n-butoxy, t-butoxy, n-pentyloxy, neopentyloxy, linear or branched alkoxy groups such as n-hexyloxy groups; cyclopropyloxy, cyclobutyloxy, Examples include cyclic alkoxy groups such as cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy groups.

In compound (1) or (2), the "aryloxy group" is not particularly limited, and examples thereof include phenoxy, biphenyloxy, naphthoxy groups, and the like.

In compound (1) or (2), the "alkylthio group" is not particularly limited, and examples thereof include methylthio group, ethylthio group, and n-propylthio group.

In compound (1) or (2), the "arylthio group" is not particularly limited, and examples thereof include phenylthio group, naphthylthio group, biphenylthio group, and the like.

Among the compounds represented by formula (1), compounds in which R ¹ is a hydrogen atom are preferred.

Among the compounds represented by formula (1), compounds in which R ² is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, an aralkyl group, an aryl group, or a heterocyclic group are preferred. , a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a benzyl group, a phenyl group, a naphthyl group, or a furyl group are more preferable; More preferred are compounds that are linear alkyl groups.

Among the compounds represented by formula (1), compounds in which at least one of R ³ and R ⁴ is a hydrogen atom are preferred, and compounds in which both R ³ and R ⁴ are hydrogen atoms are more preferred.

Among the compounds represented by formula (1), R ¹ is a hydrogen atom, R ² is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, an aralkyl group, an aryl group, or a hetero A compound in which R ³ and R ⁴ are both hydrogen atoms, a ring group, and a linear or branched alkyl group having 1 to 4 carbon atoms, in which R ¹ is a hydrogen atom, R ² is a hydrogen atom, More preferably, the compound is an aralkyl group, an aryl group, or a heterocyclic group, and R ³ and R ⁴ are combined to form an alkylidene group, R ¹ is a hydrogen atom, and R ² is a hydrogen atom or Particularly preferred are compounds in which the alkyl group is a linear alkyl group having 1 to 4 carbon atoms, and R ³ and R ⁴ are both hydrogen atoms.

Among the compounds represented by formula (2), R ⁵ is a hydrogen atom, R ⁶ is a linear or branched alkyl group having 1 to 4 carbon atoms, an aralkyl group, or an aryl group, and R ⁷ and R ⁸ are the same or different and are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, an aralkyl group, an aryl group, an amino group, or a heterocyclic group.

Among the compounds represented by formula (2), compounds in which R ⁶ is a linear alkyl group having 1 to 4 carbon atoms, an aralkyl group, or an aryl group are preferred; , or an aryl group is more preferred.

Among the compounds represented by formula (2), compounds in which R ⁷ and R ⁸ are the same or different and are a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or an amino group are preferred.

Among the compounds represented by formula (2), R ⁵ is a hydrogen atom, R ⁶ is a linear alkyl group having 1 to 4 carbon atoms, or an aryl group, and R ⁷ and R ⁸ are the same or different. Preferably, the compound is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or an amino group.

Among compound (1) and compound (2), compound (1) is particularly preferred.

Examples of compound (1) include 5-pyrazolone, 3-methyl-5-pyrazolone, 3-(naphthalen-2-yl)-1H-pyrazol-5(4H)-one, 3-(furan-2-yl) )-1H-pyrazol-5(4H)-one, 3-phenyl-1H-pyrazol-5(4H)-one, 3-propyl-1H-pyrazol-5(4H)-one, 3-t-butyl-1H -pyrazol-5(4H)-one, 3-undecyl-1H-pyrazol-5(4H)-one, 4-(2-hydroxyethyl)-3-methyl-1H-pyrazol-5(4H)-one, 4 -benzyl-3-methyl-1H-pyrazol-5(4H)-one, 4,4'-(phenylmethylene)bis(5-methyl-1H-pyrazol-3(2H)-one), 4-[(dimethylamino) ) methylidene]-3-methyl-1H-pyrazol-5(4H)-one, 4-methyl-2,3-diazospiro[4.4]non-3en-1-one, 5-methyl-2-(4 -nitrophenyl)-1H-pyrazol-3(2H)-one, 5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 4,5,6,7-tetrahydro-2H- Indazol-3(3aH)-one, 4-{[4-dimethylamino]phenyl}methylidene}-3-methyl-1H-pyrazol-5(4H)-one, 4,4'-(4-hydroxyphenylmethylene) bis(5-methyl-1H-pyrazol-3(2H)-one), 1,3-diphenyl-1H-pyrazol-5(4H)-one, and 4,4'-(4-nitrophenylmethylene)bis( 5-methyl-1H-pyrazol-3(2H)-one) and the like.

Examples of compound (2) include 1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one, 1-phenyl-1H-pyrazol-3(2H)-one, and 4-amino- Examples include 1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one.

Among them, a preferred compound is compound (1), among which 5-pyrazolone, 3-methyl-5-pyrazolone, 3-(naphthalen-2-yl)-1H-pyrazol-5(4H)-one, 3 -(furan-2-yl)-1H-pyrazol-5(4H)-one, 3-phenyl-1H-pyrazol-5(4H)-one, and 3-propyl-1H-pyrazol-5(4H)-one is more preferred, and 5-pyrazolone and 3-methyl-5-pyrazolone are particularly preferred.

Component (a) in the foaming ratio improver for polymeric materials of the present invention may contain only one type of the compounds described above as compounds (1) and (2), or may contain a mixture of two or more. But that's fine.

Some compounds (1) or (2) generate tautomers. When tautomerization is possible (eg, in solution), a chemical equilibrium of tautomers can be reached. Compound (1) or (2) can exist, for example, as a tautomer as represented by formulas (3) to (9).

In the above formula (1), the compound (compound (1)-A) in which R ¹ and R ³ are hydrogen atoms has tautomers represented by the following formulas (4) to (6). .

（式中、Ｒ^２及びＲ^４は、前記に同じ。）

(In the formula, R ² and R ⁴ are the same as above.)

In the above formula (1), the compound (compound (1)-B) in which R ³ is a hydrogen atom has tautomers represented by the following formulas (7) to (8).

（式中、Ｒ^１、Ｒ^２及びＲ^４は、前記に同じ。）

(In the formula, R ¹ , R ² and R ⁴ are the same as above.)

In the above formula (1), the compound (compound (1)-C) in which R ¹ is a hydrogen atom has a tautomer represented by the following formula (9).

（式中、Ｒ^２、Ｒ^３及びＲ^４は、前記に同じ。）

(In the formula, R ² , R ³ and R ⁴ are the same as above.)

In the above formula (2), the compound (compound (2)-A) in which R ⁵ is a hydrogen atom has a tautomer represented by the following formula (10).

（式中、Ｒ^６、Ｒ^７及びＲ^８は、前記に同じ。）

(In the formula, R ⁶ , R ⁷ and R ⁸ are the same as above.)

The tautomers represented by formulas (4) to (10) above and compound (1) or (2) have reached an equilibrium state in which both isomers coexist. Therefore, unless otherwise stated herein, all tautomeric forms of compound (1) or (2) are within the scope of the present invention.

The salt of the compound represented by formula (1) or (2) is not particularly limited and includes all kinds of salts. Examples of such salts include inorganic acid salts such as hydrochloride, sulfate, and nitrate; organic acid salts such as acetate and methanesulfonate; alkali metal salts such as sodium salt and potassium salt; magnesium salt and calcium salt. Alkaline earth metal salts such as salts; ammonium salts such as dimethylammonium and triethylammonium; and the like.

(b) Salt component (b) is a salt.

Salts include inorganic salts and organic acid salts.

Examples of inorganic salts include carbonates such as calcium carbonate, barium carbonate, magnesium carbonate, lithium carbonate, strontium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, zinc carbonate, calcium phosphate, magnesium phosphate, sodium phosphate, potassium phosphate, These are phosphates such as barium phosphate, sulfates such as sodium sulfate, potassium sulfate, barium sulfate, calcium sulfate, magnesium sulfate, lithium sulfate, strontium sulfate, and zinc sulfate, and silicates such as talc, clay, and mica. Among these, carbonates are preferred, and calcium carbonate and magnesium carbonate are particularly preferred.

Examples of organic acid salts include sodium citrate, potassium citrate, calcium citrate, magnesium citrate, magnesium oxalate, sodium oxalate, potassium oxalate, sodium tartrate, potassium tartrate, calcium stearate, calcium palmitate, calcium laurate, etc. can be mentioned. Among these, calcium citrate, magnesium citrate, magnesium oxalate, and calcium stearate are more preferred.

The above salts can be used alone or in a mixture (blend) of two or more.

The foaming ratio improver for polymer materials of the present invention contains a pyrazolone compound such as 3-methyl-5-pyrazolone and salts such as calcium carbonate, and when using a chemical foaming agent such as baking soda (sodium hydrogen carbonate), In a foam using a polymer material, the expansion ratio of the foam can be improved and the cells in the foam can be made finer.

The foaming ratio improver for polymeric materials of the present invention contains a pyrazolone compound such as 3-methyl-5-pyrazolone and salts such as calcium carbonate, and when a chemical foaming agent such as baking soda is used, a chemical foaming agent is used. In the foaming agent composition for polymeric materials, even if the composition is stored for a long time, deterioration in foaming performance and coloration of the composition can be suppressed.

Compounding ratio Component (a) in the foaming ratio improver for polymeric materials may include a mixture containing compound (1) or compound (2) in any proportion.

The content of component (a) (pyrazolone compound) in the foaming ratio improver for polymeric materials (100 parts by mass) is preferably 10% by mass to 90% by mass, and preferably 30% to 70% by mass. It is more preferable that the amount is 40% by mass to 60% by mass.

By adjusting the content of component (a) in the foaming ratio improver for polymeric materials to 10% by mass to 90% by mass, the foaming ratio of the foam can be improved, and the bubbles in the foam can be improved. can be made finer, and even if the composition is stored for a long period of time, the deterioration in foaming performance and coloration of the composition can be suppressed.

The content of component (b) (salts) in the foaming ratio improver for polymeric materials (100 parts by mass) is preferably 10% by mass to 90% by mass, preferably 30% by mass to 70% by mass. The content is more preferably 40% by mass to 60% by mass.

By adjusting the content of component (b) in the foaming ratio improver for polymeric materials to 10% by mass to 90% by mass, the foaming ratio of the foam can be improved, and the bubbles in the foam can be improved. can be made finer, and even if the composition is stored for a long period of time, the deterioration in foaming performance and coloration of the composition can be suppressed.

[2] Blowing agent composition for polymeric materials The blowing agent composition for polymeric materials of the present invention is
The foaming ratio improver for polymeric materials, and (c) a chemical foaming agent are included.

In other words, the blowing agent composition for polymeric materials of the present invention includes (a) at least one compound selected from compounds represented by formulas (1) and (2), and salts of the compounds:

（式（１）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は同一又は異なって、水素原子、アルキル基、アラルキル基、アリール基、又は複素環基を示す。Ｒ^３とＲ^４とは互いに結合してアルキリデン基を形成してもよく、Ｒ^２、Ｒ^３及びＲ^４のいずれか２つが互いに結合してアルキレン基を形成してもよい。これら各基は、それぞれ１個以上の置換基を有していてもよい。）

(In formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group. What are R ³ and R ⁴ ? They may be combined with each other to form an alkylidene group, or any two of R ² , R ³ and R ⁴ may be combined with each other to form an alkylene group. Each of these groups has one or more substituents. (It may have a group.)

（式（２）中、Ｒ^５、Ｒ^７及びＲ^８は同一又は異なって、水素原子、アミノ基、アルキル基、アラルキル基、アリール基、又は複素環基を示し、Ｒ^６はアルキル基、アラルキル基、アリール基、又は複素環基を示す。これら各基は、それぞれ１個以上の置換基を有していてもよい。）
（ｂ）塩類、及び
（ｃ）化学発泡剤を含む。

(In formula (2), R ⁵ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, an amino group, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and R ⁶ is an alkyl group, an aralkyl group. group, aryl group, or heterocyclic group. Each of these groups may have one or more substituents.)
(b) salts; and (c) chemical blowing agents.

(c) Chemical blowing agent Component (c) is a chemical blowing agent.

The foaming ratio improver for polymeric materials of the present invention can be used as a foaming agent composition for polymeric materials to impart excellent foaming ratio and fine (dense) cells to polymeric materials by using a chemical blowing agent in combination. can do.

The chemical blowing agent is not particularly limited, and a wide variety of known chemical blowing agents can be used.

Chemical blowing agents include azodicarbonamide, N,N'-dinitrosopentane methylenetetramine, p,p'-oxybisbenzenesulfonyl hydrazide, para-toluenesulfonyl hydrazide, p-toluenesulfonyl semicarbazide, diazoaminobenzene, hydrazodicarbonate. Examples include organic chemical blowing agents such as organic acids such as amide, barium azodicarboxylate, azobisisobutyronitrile, and monosodium citrate, and metal salts thereof.

Examples of the chemical blowing agent include inorganic chemical blowing agents such as baking soda (sodium hydrogen carbonate), ammonium hydrogen carbonate, sodium carbonate, ammonium carbonate, aluminum acetate, ammonium nitrite, and sodium borohydride.

The above chemical blowing agents can be used alone or in a mixture (blend) of two or more.

The surface of these foaming agents may be chemically treated. Such a blowing agent is excellent in terms of prevention of solidification, dispersibility, dust suppression, processability, storage stability, etc. of the blowing agent. Furthermore, compositions and foams obtained using such blowing agents are excellent in terms of improved mechanical properties, finer bubbles, and the like.

Among the above chemical blowing agents, azodicarbonamide, p,p'-oxybisbenzenesulfonyl hydrazide, and sodium bicarbonate are preferred, with sodium bicarbonate being particularly preferred.

The median diameter of azodicarbonamide (ADCA) is preferably about 1 μm to 40 μm, more preferably 2 μm to 25 μm, and still more preferably 4 μm to 20 μm. By using azodicarbonamide with a median diameter of about 1 μm to 40 μm, it is possible to obtain a foam having a high expansion ratio and fine (dense) cells in a blowing agent composition for polymer materials.

Foaming aid The foaming ratio improver for polymeric materials of the present invention may be used in combination with a foaming aid.

The foaming aid is not particularly limited, and any commonly used foaming aid known in the art can be used.

Foaming aids include urea, mixtures of urea and fatty acids and fatty acid metal salts; urea compounds such as thiourea, tetramethylurea, dimethylthiourea, semicarbazide, and carbohydrazide, zinc oxide, zinc stearate, zinc benzenesulfinate, and toluene. Examples include zinc compounds such as zinc sulfonate, zinc trifluoromethanesulfonate, and zinc carbonate, lead compounds such as lead dioxide, and tribasic lead, among which zinc oxide, zinc stearate, zinc benzenesulfinate, and zinc carbonate. Preference is given to using zinc.

The above-mentioned foaming aids can be used alone or in a mixture (blend) of two or more.

Compounding ratio In the blowing agent composition for polymeric materials of the present invention (100 parts by mass), the content of component (c) chemical blowing agent is preferably 1% by mass to 99% by mass, and preferably 60% by mass to It is more preferably 95% by mass, and even more preferably 70% by mass to 90% by mass.

By adjusting the content of component (c) chemical blowing agent in the blowing agent composition for polymeric materials of the present invention to 1% by mass to 99% by mass, the expansion ratio of the foam can be improved. It is possible to make the cells of the foam finer, and even if the composition is stored for a long period of time, it is possible to suppress the deterioration of the foaming performance and coloration of the composition.

[3] Polymer composition The polymer composition of the present invention is:
The foaming agent composition for a polymeric material, and (d) a polymeric material.

In other words, the polymer composition of the present invention has the following characteristics:
(a) At least one compound selected from compounds represented by formulas (1) and (2), and salts of the compounds:

（式（１）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は同一又は異なって、水素原子、アルキル基、アラルキル基、アリール基、又は複素環基を示す。Ｒ^３とＲ^４とは互いに結合してアルキリデン基を形成してもよく、Ｒ^２、Ｒ^３及びＲ^４のいずれか２つが互いに結合してアルキレン基を形成してもよい。これら各基は、それぞれ１個以上の置換基を有していてもよい。）

(In formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group. What are R ³ and R ⁴ ? They may be combined with each other to form an alkylidene group, or any two of R ² , R ³ and R ⁴ may be combined with each other to form an alkylene group. Each of these groups has one or more substituents. (It may have a group.)

（式（２）中、Ｒ^５、Ｒ^７及びＲ^８は同一又は異なって、水素原子、アミノ基、アルキル基、アラルキル基、アリール基、又は複素環基を示し、Ｒ^６はアルキル基、アラルキル基、アリール基、又は複素環基を示す。これら各基は、それぞれ１個以上の置換基を有していてもよい。）
（ｂ）塩類
（ｃ）化学発泡剤、及び
（ｄ）高分子材料を含む。

(In formula (2), R ⁵ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, an amino group, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and R ⁶ is an alkyl group, an aralkyl group. group, aryl group, or heterocyclic group. Each of these groups may have one or more substituents.)
(b) salts, (c) chemical blowing agents, and (d) polymeric materials.

(d) Polymeric material Component (d) is a polymeric material.

The polymeric material that can be applied to the blowing agent composition for polymeric materials of the present invention is not particularly limited, and a wide variety of known polymeric materials can be used.

Examples of the polymer material include rubber, resin (thermosetting resin, thermoplastic resin, etc.).

The rubber is not particularly limited and includes, for example, diene rubber, non-diene rubber, and a mixture of diene rubber and non-diene rubber.

Examples of diene rubber include natural rubber (NR), styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), styrene-isoprene-butadiene rubber (SIBR), and nitrile rubber (NBR). , chloroprene rubber (CR), styrene-isoprene-styrene triblock copolymer (SIS), styrene-butadiene-styrene triblock copolymer (SBS), and modified diene rubbers thereof. Among the diene rubbers, natural rubber, butadiene rubber, and styrene-butadiene copolymer rubber are preferred.

Examples of natural rubber include natural rubber latex, technically graded rubber (TSR), smoked sheet (RSS), gutta-percha, natural rubber derived from mori, natural rubber derived from guayule, and natural rubber derived from Russian dandelion.

Modified natural rubbers such as epoxidized natural rubber, methacrylic acid-modified natural rubber, halogen-modified natural rubber, deproteinized natural rubber, maleic acid-modified natural rubber, sulfonic acid-modified natural rubber, styrene-modified natural rubber, etc. It is also preferable to use

The modified diene rubber includes diene rubbers obtained by modification methods such as main chain modification, one end modification, and both end modification. The modified functional groups of the modified diene rubber include various functional groups such as epoxy groups, amino groups, alkoxysilyl groups, and hydroxyl groups, and one or more of these functional groups are contained in the modified diene rubber. It's okay.

The method for producing diene rubber is not particularly limited, and examples include emulsion polymerization, solution polymerization, radical polymerization, anionic polymerization, and cationic polymerization. Furthermore, there is no particular restriction on the glass transition point of the synthetic diene rubber.

Non-diene rubbers include butyl rubber (IIR), ethylene-propylene rubber (EPM), ethylene-propylene-diene terpolymer rubber (EPDM), urethane rubber (U), propylene hexafluoride-vinylidene fluoride, etc. polymer (FKM), tetrafluoroethylene-propylene copolymer (FEPM), tetrafluoroethylene-perfluorovinylether copolymer (FFKM), methyl silicone rubber (MQ), vinyl methyl silicone rubber (VMQ), phenyl Examples include methyl silicone rubber (PMQ), acrylic rubber (ACM), polysulfide rubber (T), epichlorohydrin rubber (CO, ECO), and modified non-diene rubbers thereof. Among these, butyl rubber and ethylene-propylene-diene terpolymer rubber (EPDM) are preferred.

The modified non-diene rubber includes non-diene rubber that has been modified by main chain modification, one end modification, both end modification, and the like. Here, the modified functional groups of the modified non-diene rubber include various functional groups such as epoxy groups, amino groups, alkoxysilyl groups, and hydroxyl groups, and one or more of these functional groups are It may be included in rubber.

The method for producing the non-diene rubber is not particularly limited, and examples thereof include emulsion polymerization, solution polymerization, radical polymerization, anionic polymerization, and cationic polymerization. Furthermore, there is no particular restriction on the glass transition point of the synthetic non-diene rubber.

There is no particular restriction on the cis/trans/vinyl ratio of the double bond in natural rubber and diene rubber, and any ratio can be suitably used. Further, there are no particular limitations on the number average molecular weight and molecular weight distribution of the diene rubber, and preferably a number average molecular weight of 500 to 3,000,000 and a molecular weight distribution of 1.5 to 15. As the non-diene rubber, a wide variety of known rubbers can be used.

Rubbers can be used alone or in a mixture (blend) of two or more.

Among rubbers, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), nitrile rubber (NBR), and ethylene-propylene-diene terpolymer rubber (EPDM) is preferably used.

The resin is not particularly limited, and examples thereof include thermosetting resins, thermoplastic resins, and the like.

Examples of the thermosetting resin include polyurethane, epoxy resin, phenol resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, thermosetting polyimide, and the like.

Thermoplastic resins include polyethylene, polypropylene, polyvinyl chloride, ethylene-vinyl acetate copolymer, polystyrene, polyvinyl acetate, polyurethane, polytetrafluoroethylene, acrylonitrile-butadiene-styrene resin, acrylonitrile-styrene resin, acrylic resin, Examples include polyvinyl alcohol.

The resins can be used alone or in a mixture (blend) of two or more.

Among these resins, polyethylene, polypropylene, polyvinyl chloride, ethylene-vinyl acetate copolymer, and polyurethane are preferred, and polyethylene is more preferred.

Polyethylene As polyethylene (PE), low-density polyethylene, medium-density polyethylene, high-density polyethylene, etc. can be used, but preferably low-density polyethylene, more preferably (branched) low-density polyethylene (LDPE), Linear low density polyethylene (LLDPE) or the like is used.

By using low density polyethylene (LDPE) for the blowing agent composition for polymeric materials of the present invention, a foam having a high expansion ratio and fine (dense) cells can be obtained.

Low density polyethylene (LDPE) is preferably, for example, low density polyethylene polymerized with a metallocene catalyst, high pressure low density polyethylene (HP-LDPE) produced by high pressure radical polymerization using a radical initiator, transition metal catalyst. Linear low-density polyethylene (LLDPE) produced by coordination ion polymerization is used.

Low density polyethylene (LDPE)
The melt mass flow rate (MFR) of LDPE is based on Japanese Industrial Standard JIS K 7210-1:2014 (ISO 1133-1:2011) Plastics - Determination of melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics. - Part 1: Values according to standard test methods. MFR is expressed in grams per 10 minutes (g/10min).

The MFR of LDPE is preferably about 0.1 g/10 min to 50 g/10 min, more preferably about 1 g/10 min to 20 g/10 min, and still more preferably about 2 g/10 min to 10 g/10 min. It is particularly preferably about 3 g/10 min to 5 g/10 min. By using LDPE with an MFR of about 0.1 g/10 min to 50 g/10 min in the blowing agent composition for polymer materials of the present invention, a foam having a high expansion ratio and fine (dense) cells can be produced. You can get it.

The density (kg/m ³ ) of LDPE is a value according to Japanese Industrial Standards JIS K 7112:1999 Plastics - Method for measuring density and specific gravity of non-foamed plastics.

The density of LDPE is preferably about 900 kg/m ³ to 950 kg/m ³ , more preferably about 910 kg/m ³ to 940 kg/m ³ , even more preferably 920 kg/m ³ to 930 kg/m 3 It is about ³ . By using LDPE with a density of about 900 kg/m ³ to 950 kg/m ³ in the foaming agent composition for polymeric materials of the present invention, a foam having a high expansion ratio and fine (dense) cells can be produced. You can get it.

Compounding ratio In the polymer composition of the present invention, the amount of (a) compounds (1) and (2) (pyrazolone compounds) used is 0.01 part by mass to 100 parts by mass of (d) polymer material. The amount is preferably 10 parts by weight, more preferably 0.1 parts to 5 parts by weight, and even more preferably 0.5 parts to 2 parts by weight.

In the polymer composition of the present invention, the amount of (a) compounds (1) and (2) (pyrazolone compounds) to be used is 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of (d) polymer material. When the polymer composition is foamed, it is possible to improve the foaming ratio of the foam and to make the cells of the foam finer, and even when the composition is stored for a long time, Coloring of the composition can be suppressed.

In the polymer composition of the present invention, the amount of (b) salt used is preferably 0.01 parts by mass to 10 parts by mass, and 0.1 parts by mass, based on 100 parts by mass of (d) polymer material. The amount is more preferably 0.5 parts to 5 parts by weight, and even more preferably 0.5 parts to 2 parts by weight.

In the polymer composition of the present invention, the amount of the (b) salt used is adjusted to 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the (d) polymer material. When foaming a product, the expansion ratio of the foam can be improved, the cells in the foam can be made finer, and the coloring of the composition can be suppressed even when the composition is stored for a long time.

In the polymer composition of the present invention, the amount of (c) chemical blowing agent used is preferably 1 part by mass to 30 parts by mass, and preferably 5 parts by mass to 100 parts by mass of (d) polymer material. It is more preferably 25 parts by mass, and even more preferably 10 to 20 parts by mass.

In the polymer composition of the present invention, the amount of (c) chemical blowing agent used is adjusted to 1 part by mass to 30 parts by mass with respect to 100 parts by mass of (d) polymer material. When foaming something, it is possible to improve the foaming ratio of the foam, make the cells in the foam finer, and suppress the deterioration of the foaming performance and coloration of the composition even if the composition is stored for a long time. I can do things.

[4] Other compounding agents The foaming ratio improver for polymeric materials, the blowing agent composition for polymeric materials, and the polymeric composition of the present invention preferably contain crosslinking agents, carbon black, inorganic fillers (silica, etc.). ), silane coupling agents, anti-aging agents, anti-ozonants, softeners, processing aids, waxes, oils, fatty acids with 8 to 30 carbon atoms (stearic acid, etc.), fatty acid metal salts, zinc oxide (ZnO), additives Sulfur accelerator, vulcanization retarder, vulcanizing agent (sulfur, etc.), crosslinking aid, crosslinking agent, pigment, dye, tackifier, bubble nucleating agent, odor absorbent, ultraviolet absorber, light stabilizer, oxidation Inhibitor, light shielding agent, metal deactivator, quencher, antifog agent, antifungal agent, antibacterial agent, deodorant, plasticizer, antistatic agent, surfactant, polymerization inhibitor, sensitizer, curing accelerator , diluent, fluidity regulator, leveling agent, adhesive, adhesive, lubricant, mold release agent, lubricant, solid lubricant, reinforcing agent, compatibilizer, conductive agent, anti-blocking agent, anti-tracking agent, luminescent A flame retardant, a dispersant, etc. are appropriately selected and blended.

The crosslinking agent is preferably dicumyl peroxide (DCP), benzoyl peroxide, dihexyl peroxide, di-t-butylperoxydi-isopropylbenzene, 2,5-dimethyl-2,5-di -(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(t-butylperoxy)hexyne-3, p-benzoquinone dioxime, lead oxide, zinc oxide, mercaptobenzothiazole, 2 , 2'-Dibenzothiazolyl disulfide, dipentamethylenethiuram tetrasulfide, tetrabutylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram disulfide, N-cyclohexyl-2-benzothiazolylsulfenamide, N-t-butyl- 2-Benzothiazolylsulfenamide, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc N-pentamethylenedithiocarbamate, zinc dibenzyldithiocarbamate, dibutyl Sodium dithiocarbamate, copper dimethyldithiocarbamate, tellurium diethyldithiocarbamate, 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, 1,3-di-o-tolylguanidine salt of dicatecholborate, hexamethylene Tetramine etc. More preferably, the crosslinking agent is dicumyl peroxide.

The crosslinking agent may be used singly or in combination of two or more types.

The carbon black is not particularly limited, and examples thereof include commercially available carbon black, Carbon-Silica dual phase filler, and the like.

Examples of carbon black include high, medium or low structure SAF, ISAF, IISAF, N110, N134, N220, N234, N330, N339, N375, N550, HAF, FEF, GPF, SRF grade carbon black, etc. It will be done. Among them, preferred carbon blacks are SAF, ISAF, IISAF, N134, N234, N330, N339, N375, HAF, or FEF grade carbon black.

The DBP absorption amount of carbon black is not particularly limited, and is preferably 60cm ³ /100g to 200cm ³ /100g, more preferably 70cm ³ /100g to 180cm ³ /100g, particularly preferably 80cm ³ /100g to 160cm ^{3 /} 100g. It is 100g.

Further, the nitrogen adsorption specific surface area of carbon black (measured according to N2SA, JISK6217-2:2001) is preferably 30 m ² /g to 200 m ² /g, more preferably 40 m ² /g to 180 m ² /g. , particularly preferably from 50 m ² /g to 160 m ² /g.

The inorganic filler (inorganic compound) is not particularly limited and includes, for example, silica; alumina _{(Al 2 O 3 ) such as γ-alumina and α-alumina; alumina monohydrate (Al 2 O 3} ) such as boehmite and diaspore; _{3.H 2} O); aluminum hydroxide [Al(OH) ₃ ] such as gibbsite and bayerite; aluminum carbonate [Al ₂ (CO ₃ ) ₃ ], magnesium hydroxide [Mg(OH) ₂ ], magnesium oxide ( MgO), magnesium carbonate (MgCO ₃ ), talc (3MgO・4SiO ₂・H ₂ O), attapuljium (5MgO・8SiO ₂・9H ₂ O), titanium white (TiO ₂ ), titanium black (TiO _2n-1 ), Calcium oxide (CaO), calcium hydroxide [Ca(OH) ₂ ], magnesium aluminum oxide (MgO・Al ₂ O ₃ ), clay (Al ₂ O ₃・2SiO ₂ ), kaolin (Al ₂ O ₃・2SiO ₂・2H ₂ O), pyrophyllite (Al ₂ O _3.4SiO 2.H ₂ O), bentonite (Al _{2 O} 3.4SiO _{2.2H 2} O), aluminum silicate ₍ Al ₂ SiO ₅ , Al _{4.3SiO 4}・5H ₂ O, etc.), magnesium silicate (Mg ₂ SiO ₄ , MgSiO ₃ , etc.), calcium silicate (Ca ₂・SiO _4, etc.), aluminum calcium silicate (Al ₂ O ₃・CaO ・2SiO _2, etc.) , magnesium calcium silicate (CaMgSiO ₄ ), zirconium oxide (ZrO ₂ ), zirconium hydroxide [ZrO(OH) ₂ ·nH ₂ O], zirconium carbonate [Zr(CO ₃ ) ₂ ], zinc acrylate, zinc methacrylate , crystalline aluminosilicates containing hydrogen, alkali metals, or alkaline earth metals that correct charge, such as various zeolites.

The surface of these inorganic fillers may be organically treated in order to improve their affinity with polymeric materials.

Any commercially available silica can be used. Among these, preferable silica is wet silica, dry silica, or colloidal silica, and wet silica is more preferable. The surface of these silicas may be organically treated in order to improve the affinity with the rubber component.

There is no particular limitation on the BET specific surface area of silica, and for example, a range of 40 m ² /g to 350 m ² /g can be mentioned. Silica having a BET specific surface area within this range has the advantage of being compatible with dispersibility in polymeric materials. The BET specific surface area is measured in accordance with ISO5794/1.

Preferred silica is silica having a BET specific surface area of 80 m ² /g to 300 m ² /g, more preferably silica having a BET specific surface area of 100 m ² /g to 270 m ² /g, particularly preferably is silica having a BET specific surface area in the range of 110 m ² /g to 270 m ² /g.

Commercially available silica products include Quechen Silicon Chemical Co. , Ltd. Product names "HD165MP" (BET specific surface area = 165 m ² /g), "HD115MP" (BET specific surface area = 115 m ² /g), "HD200MP" (BET specific surface area = 200 m ² /g), "HD250MP" ( BET specific surface area = 250 m ² /g), product name "Nip Seal AQ" manufactured by Tosoh Silica Co., Ltd. (BET specific surface area = 205 m ² /g), "Nip Seal KQ" (BET specific surface area = 240 m ² /g), Degussa For example, "Ultrasil VN3" (BET specific surface area = 175 m ² /g) manufactured by Co., Ltd. under the trade name of "Ultrasil VN3".

When blending carbon black and/or inorganic fillers (silica, etc.), silane coupling agents, titanate coupling agents, aluminate cups are used for the purpose of increasing the strength of the polymer material by carbon black and/or inorganic fillers. A ring agent and a zirconate coupling agent may be added.

The silane coupling agent is not particularly limited, and examples thereof include sulfide-based, polysulfide-based, thioester-based, thiol-based, olefin-based, epoxy-based, amino-based, and alkyl-based silane coupling agents.

Examples of sulfide-based silane coupling agents include bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(3-methyldimethoxysilylpropyl)tetrasulfide, and bis(3-trimethoxysilylpropyl)tetrasulfide. 2-triethoxysilylethyl)tetrasulfide, bis(3-triethoxysilylpropyl)disulfide, bis(3-trimethoxysilylpropyl)disulfide, bis(3-methyldimethoxysilylpropyl)disulfide, bis(2-triethoxysilyl) ethyl)disulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-trimethoxysilylpropyl)trisulfide, bis(3-methyldimethoxysilylpropyl)trisulfide, bis(2-triethoxysilylethyl)trisulfide Sulfide, bis(3-monoethoxydimethylsilylpropyl)tetrasulfide, bis(3-monoethoxydimethylsilylpropyl)trisulfide, bis(3-monoethoxydimethylsilylpropyl)disulfide, bis(3-monomethoxydimethylsilylpropyl) Tetrasulfide, bis(3-monomethoxydimethylsilylpropyl)trisulfide, bis(3-monomethoxydimethylsilylpropyl)disulfide, bis(2-monoethoxydimethylsilylethyl)tetrasulfide, bis(2-monoethoxydimethylsilylethyl) ) trisulfide, bis(2-monoethoxydimethylsilylethyl) disulfide, and the like. Among these, bis(3-triethoxysilylpropyl)tetrasulfide is particularly preferred.

Examples of thioester-based silane coupling agents include 3-hexanoylthiopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-decanoylthiopropyltriethoxysilane, and 3-lauroylthiopropyltriethoxysilane. , 2-hexanoylthioethyltriethoxysilane, 2-octanoylthioethyltriethoxysilane, 2-decanoylthioethyltriethoxysilane, 2-lauroylthioethyltriethoxysilane, 3-hexanoylthiopropyltrimethoxysilane, 3-octanoylthiopropyltrimethoxysilane, 3-decanoylthiopropyltrimethoxysilane, 3-lauroylthiopropyltrimethoxysilane, 2-hexanoylthioethyltrimethoxysilane, 2-octanoylthioethyltrimethoxysilane, 2 -decanoylthioethyltrimethoxysilane, 2-lauroylthioethyltrimethoxysilane and the like.

Examples of thiol-based silane coupling agents include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-[ethoxybis(3,6,9,12,15 -pentaoxaoctacosan-1-yloxy)silyl]-1-propanethiol and the like.

Examples of olefin-based silane coupling agents include dimethoxymethylvinylsilane, vinyltrimethoxysilane, dimethylethoxyvinylsilane, diethoxymethylvinylsilane, triethoxyvinylsilane, vinyltris(2-methoxyethoxy)silane, allyltrimethoxysilane, and allyltrimethoxysilane. Ethoxysilane, p-styryltrimethoxysilane, 3-(methoxydimethoxydimethylsilyl)propyl acrylate, 3-(trimethoxysilyl)propyl acrylate, 3-[dimethoxy(methyl)silyl]propyl methacrylate, 3-(trimethoxysilyl) Examples include propyl methacrylate, 3-[dimethoxy(methyl)silyl]propyl methacrylate, 3-(triethoxysilyl)propyl methacrylate, and 3-[tris(trimethylsiloxy)silyl]propyl methacrylate.

Examples of epoxy-based silane coupling agents include 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxypropyltrimethoxysilane, diethoxy(3-glycidyloxypropyl)methylsilane, and triethoxy(3-glycidyloxypropyl)silane. , 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and the like. Among these, 3-glycidyloxypropyltrimethoxysilane is preferred.

Examples of amino-based silane coupling agents include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-ethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)- Examples include 2-aminoethyl-3-aminopropyltrimethoxysilane. Among these, 3-aminopropyltriethoxysilane is preferred.

Examples of alkyl-based silane coupling agents include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, and isobutyltriethoxysilane. Examples include silane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, and n-decyltrimethoxysilane. Among these, methyltriethoxysilane is preferred.

Among these silane coupling agents, bis(3-triethoxysilylpropyl)tetrasulfide can be particularly preferably used.

The titanate coupling agent is not particularly limited, and examples thereof include alkoxide-based, chelate-based, and acylate-based titanate coupling agents.

Examples of the alkoxide-based titanate coupling agent include tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, tetraoctyl titanate, tetratert-butyl titanate, tetrastearyl titanate, and the like. Among these, tetraisopropyl titanate is preferred.

Examples of chelate-based titanate coupling agents include titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethyl acetoacetate, titanium dodecylbenzenesulfonic acid compounds, titanium phosphate compounds, titanium octylene glycolate, and titanium ethyl acetoacetate. , titanium lactate ammonium salt, titanium lactate, titanium ethanolaminate, titanium octylene glycolate, titanium aminoethylaminoethanolate, and the like. Among these, titanium acetylacetonate is preferred.

Examples of the acylate-based titanate coupling agent include titanium isostearate.

The aluminate coupling agent is not particularly limited, and examples of the aluminate coupling agent include 9-octadecenyl acetoacetate aluminum diisopropylate, aluminum secondary butoxide, aluminum trisacetylacetonate, and aluminum bisethyl acetoacetate. Examples include monoacetylacetonate and aluminum trisethylacetoacetate. Among these, 9-octadecenyl acetoacetate aluminum diisopropylate is preferred.

The zirconate coupling agent is not particularly limited, and examples thereof include alkoxide-based, chelate-based, and acylate-based zirconate coupling agents.

Examples of the alkoxide-based zirconium coupling agent include normal propyl zirconate and normal butyl zirconate. Among these, normal butyl zirconate is preferred.

Examples of chelate-based zirconate coupling agents include zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium ethyl acetoacetate, and zirconium lactate ammonium salt. Among these, zirconium tetraacetylacetonate is preferred.

Examples of the acylate-based zirconate coupling agent include zirconium stearate and zirconium octylate. Among these, zirconium stearate is preferred.

In the present invention, one type of silane coupling agent, titanate coupling agent, aluminate coupling agent, and zirconate coupling agent may be used alone, or two or more types may be used in combination.

[5] Foam The foam of the present invention is produced by foaming the polymer composition.

By foaming the polymer composition, the foaming ratio can be improved and the cells can be made finer (densified).

The foamed body also includes an embodiment in which it is formed into a molded body by molding.

The foam of the present invention has an improved expansion ratio and finer cells, and is useful as a foam that is widely used in building materials, automobile parts, industrial parts, and the like. Improving the expansion ratio of the foam leads to a reduction in the amount of polymer material used in the foam, which leads to a reduction in CO ₂ emissions.

The foam of the present invention has a high degree of social contribution from an environmental point of view.

Production of rubber foams using rubber components such as ethylene-propylene-diene terpolymer rubber (EPDM), and production of foams using resin components such as (branched) low-density polyethylene (LDPE). Now, kneading methods are diversifying.

When a composition containing a chemical blowing agent and a pyrazolone compound such as 3-methyl-5-pyrazolone is foamed, the expansion ratio of the foam increases compared to when a pyrazolone compound such as 3-methyl-5-pyrazolone is not used. and the bubbles become finer.

When an (inorganic) chemical blowing agent such as baking soda and a pyrazolone compound such as 3-methyl-5-pyrazolone are used together, the mixture becomes colored due to the hygroscopicity of the baking soda, and the 3-methyl-5-pyrazolone Alteration, deterioration, etc. may occur, and the foaming performance may also be affected (decreased).

In the present invention, by mixing a pyrazolone compound such as 3-methyl-5-pyrazolone with a salt such as calcium carbonate, a foaming ratio improver for polymeric materials, a blowing agent composition for polymeric materials, and a polymeric composition can be obtained. The present invention is useful in that it can suppress deterioration in foaming performance and coloring in , and foams, and can suppress deterioration in foaming performance.

The foam of the present invention is preferably used as a heat insulating material, a curing material, a joint material (sealing material), a door material, a covering material, a water barrier material, a sound insulating material, a floater, a cushioning material, a shock absorbing material, and a rug core. materials, toys, tires, acoustic components, hoses, belts, electrical wire coatings, etc.

The heat insulating material is, for example, a heat insulating material for piping for transporting refrigerant, heat medium, etc., and a heat insulating material for floors, walls, etc.

Examples of the joint material (sealing material) include rubber packing, oil seals, water stop materials, sealing materials, weather strips, glass run channels, and the like.

Examples of tires include pneumatic tires (radial tires, bias tires, etc.), solid tires, and the like. Examples of the tire include tires for passenger cars, tires for heavy loads, tires for motorcycles, studless tires, etc. Among them, studless tires can be suitably used. In tires, it is particularly used for at least one member selected from the tread section, sidewall section, bead area section, belt section, carcass section, and shoulder section.

Examples of the acoustic member include a speaker edge, a sound absorbing material, a sound insulating material, a vibration isolating material, a vibration isolating material, and the like.

Examples of hoses include radiator hoses, water hoses, and concrete transport hoses.

Examples of the belt include a power transmission belt, a conveyor belt, and a V-belt.

Examples of the electric wire coating include coatings for power transmission lines.

[6] Foaming ratio improver for polymeric materials, foaming agent composition for polymeric materials, polymeric composition, and method for producing foam
Foaming ratio improver for polymeric materials The foaming ratio improver for polymeric materials of the present invention can be produced by mixing the component (a) the pyrazolone compound and the component (b) salts. Other compounding agents may be mixed with the foaming ratio improver for polymeric materials, if necessary. The order of mixing component (a) and component (b) and the order of mixing other ingredients may be set as appropriate.

Blowing agent composition for polymeric materials The blowing agent composition for polymeric materials of the present invention comprises the foaming ratio improver for polymeric materials (or component (a) and component (b)), and component (c). ) Can be manufactured by mixing a chemical blowing agent. If necessary, other compounding agents (foaming aids, etc.) may be mixed into the foaming agent composition for polymeric materials. The order of mixing the foaming ratio improver for polymeric materials (or component (a) and component (b)) and the chemical foaming agent (component (c)) and the order of mixing other compounding agents should be set as appropriate. Good.

Polymer Composition The polymer composition of the present invention comprises the blowing agent composition for polymer materials (or components (a), component (b), and component (c)), and component (d) polymer. It can be manufactured by mixing materials. Other compounding agents may be mixed into the foaming agent composition for polymeric materials, if necessary. Order of mixing blowing agent composition for polymeric materials (or component (a), component (b), and component (c)) and component (d) polymeric material, order of mixing other ingredients may be set appropriately.

When the polymer composition of the present invention is made into a rubber composition, the manufacturing method includes the above-mentioned blowing agent composition for polymer materials (or component (a), component (b), and component (c)), and component (d) polymeric material may be mixed, and if necessary, a crosslinking agent, a vulcanizing agent, and other compounding agents (vulcanization accelerator, etc.) may be mixed. The order of blending may be set as appropriate. In the method for producing a rubber composition, various compounding agents such as stearic acid, zinc oxide, and anti-aging agents can be added as necessary.

In this specification, "mixing" includes not only the mode of simply mixing, but also the mode of so-called "kneading."

Mixing can be carried out either wet or dry using a rotary ball mill, vibratory ball mill, planetary mill, paint shaker, rocking mill, rocking mixer, bead mill, fluidized mixer, stirrer, or the like. Mixing can be performed using a Banbury mixer, a roll, an intensive mixer, a kneader, a single screw extruder, a twin screw extruder, or the like. After mixing, the mixture is extruded and processed in an extrusion process to form various parts.

In the rubber composition, mixing operations may be repeated in order to uniformly disperse each component. Alternatively, a filler masterbatch rubber may be used in which a filler is added to the rubber component in advance by a wet method and/or a dry mixing method.

The rubber composition is pasted and molded on a molding machine, and then vulcanized by heating and pressurizing in a vulcanizer to obtain a vulcanized product.

Foam The foam of the present invention can be produced by foaming the polymer composition (including component (a), component (b), component (c), and component (d)). . Foams can be produced by heating a mixture of polymeric compositions to cause foaming.

The heating temperature may be at least the temperature at which the mixed component (c) chemical foaming agent decomposes, and is preferably about 50°C to 300°C, more preferably about 80°C to 250°C, and even more preferably is approximately 100°C to 200°C.

The heating time is preferably about 5 seconds to 24 hours, more preferably about 10 seconds to 12 hours, and still more preferably about 5 minutes to 3 hours.

[7] Evaluation method
Expansion Ratio Index The foam of the present invention has a larger expansion ratio than conventional foams.

The expansion ratio of the foam is evaluated based on the expansion ratio index.

The expansion ratio index is calculated based on the following formula.

Expansion ratio = specific gravity of unfoamed composition / specific gravity of foamed composition Expansion ratio index = expansion ratio of Example / expansion ratio of comparative example x 100
The larger the value of the foaming ratio index, the larger the foaming ratio, and the better the foam.

Average Cell Diameter Index The foam of the present invention has a denser cell diameter than conventional foams.

The average cell diameter of the foam is evaluated based on the average cell diameter index.

The average cell diameter index is calculated based on the following formula.

Average cell diameter is expressed according to ASTM D2842-69.

Average cell diameter index=average cell diameter of example/average cell diameter of comparative example×100
The smaller the value of the average cell diameter index, the denser the cell diameter and the better the foam.

The embodiments of the present invention have been described above.

The present invention is not limited to these examples in any way.

It goes without saying that the present invention can be implemented in various forms without departing from the gist of the invention.

Hereinafter, embodiments of the present invention will be described in more detail based on Examples.

The present invention is not limited to these.

(1) Production of foam Each component listed in Tables 1 to 4 was mixed in each proportion (parts by mass) using a Banbury mixer.

The mixture was then heated in a gear oven at 220°C to produce a foam.

(2) Expansion ratio index The expansion ratio was calculated by measuring the specific gravity before and after foam molding using an electronic hydrometer (MDS-300 manufactured by ALFA MIRAGE).

A foam of a comparative example was prepared and expressed as an index with its expansion ratio set to 100, and the expansion ratio index of the foam of the example was calculated based on the following formula.

Expansion ratio = specific gravity of unfoamed composition / specific gravity of foamed composition Expansion ratio index = expansion ratio of Example / expansion ratio of comparative example x 100
The larger the value of the foaming ratio index, the larger the foaming ratio, and the better the foam.

Expansion ratio index of Examples in Table 1 = (Expansion ratio of Examples 1-1 to 1-4)/(Expansion ratio of Comparative Example 1-1) x 100
Expansion ratio index of Examples in Table 2 = (Expansion ratio of Examples 2-1 to 2-4) / (Expansion ratio of Comparative Example 1-1) x 100
Expansion ratio index of Examples in Table 3 = (Expansion ratio of Examples 3-1 to 3-3)/(Expansion ratio of Comparative Example 3-1) x 100
Expansion ratio index of Examples in Table 4 = (Expansion ratio of Examples 4-1 to 4-3)/(Expansion ratio of Comparative Example 3-1) x 100

(3) Average cell diameter index The average cell diameter was measured in accordance with ASTM D2842-69.

A foam of a comparative example was produced, and the average cell diameter was expressed as an index with the average cell diameter set as 100, and the average cell diameter index of the foam of the example was calculated based on the following formula.

Average cell diameter is expressed according to ASTM D2842-69.

Average cell diameter index=average cell diameter of example/average cell diameter of comparative example×100
The smaller the value of the average cell diameter index, the denser the cell diameter and the better the foam.

Average cell diameter index of Examples in Table 1 = (Average cell diameter of Examples 1-1 to 1-4)/(Average cell diameter of Comparative Example 1-1) x 100
Average cell diameter index of Examples in Table 2 = (Average cell diameter of Examples 2-1 to 2-4)/(Average cell diameter of Comparative Example 1-1) x 100
Average cell diameter index of Examples in Table 3 = (Average cell diameter of Examples 3-1 to 3-3)/(Average cell diameter of Comparative Example 3-1) x 100
Average cell diameter index of Examples in Table 4 = (Average cell diameter of Examples 4-1 to 4-3)/(Average cell diameter of Comparative Example 3-1) x 100

(4) Details of each component *1: Low density polyethylene, manufactured by Sumitomo Chemical Co., Ltd., Sumikasen L-405 (MFR: 3.7g/10min (JISK7210-1), density: 924kg/m ³ (JISK7112)
*2: Dicumyl peroxide (DCP): Nihon Yushi Co., Ltd., Permil D
*3: Made by Nitto Funka Kogyo, SS#30 (specific surface area: 3,000 cm ² /g)
*4: Made by Nitto Funka Kogyo, SS#80 (specific surface area: 8,000 cm ² /g)
*5: Manufactured by Toyo Denka Kogyo, light calcium carbonate

The foam of the present invention is a foam that has a higher expansion ratio than conventional foams by mixing a pyrazolone compound such as 3-methyl-5-pyrazolone with a salt such as calcium carbonate. The foam was denser in diameter.

The foam of the present invention is produced by mixing a pyrazolone compound such as 3-methyl-5-pyrazolone with a salt such as calcium carbonate at a ratio of component (a):component (b) = 1:1, and the mixture is heated to 40°C. /85%RH/ Even after a one-month abuse test, the foam maintains its foaming performance, has a higher expansion ratio, and has a denser cell diameter than conventional foams. Ta.

The present invention provides foams that use polymeric materials when using pyrazolone compounds such as 3-methyl-5-pyrazolone, salts such as calcium carbonate, and chemical blowing agents such as baking soda. It is possible to improve the foaming ratio and make the cells of the foam finer. The present invention also makes it possible to suppress deterioration in the foaming performance of the composition even when the composition is stored for a long period of time in a foaming agent composition for polymeric materials that uses a chemical foaming agent.

Claims (6)

(a) At least one compound selected from compounds represented by formulas (1) and (2), and salts of the compounds:

(In formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group. What are R ³ and R ⁴ ? They may be combined with each other to form an alkylidene group, or any two of R ² , R ³ and R ⁴ may be combined with each other to form an alkylene group. Each of these groups has one or more substituents. (It may have a group.)

(In formula (2), R ⁵ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, an amino group, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and R ⁶ is an alkyl group, an aralkyl group. group, aryl group, or heterocyclic group. Each of these groups may have one or more substituents.)
and (b) a foaming ratio improver for polymeric materials containing salts. A foaming agent composition for polymeric materials, comprising: the foaming ratio improver for polymeric materials according to claim 1; and (c) a chemical foaming agent. (a) At least one compound selected from compounds represented by formulas (1) and (2), and salts of the compounds:

(In formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group. What are R ³ and R ⁴ ? They may be combined with each other to form an alkylidene group, or any two of R ² , R ³ and R ⁴ may be combined with each other to form an alkylene group. Each of these groups has one or more substituents. (It may have a group.)

(In formula (2), R ⁵ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, an amino group, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and R ⁶ is an alkyl group, an aralkyl group. group, aryl group, or heterocyclic group. Each of these groups may have one or more substituents.)
(b) a salt; and (c) a blowing agent composition for a polymeric material, comprising a chemical blowing agent. A blowing agent composition for a polymeric material according to claim 2 or 3, and (d) a polymeric material.
A polymer composition containing. (a) At least one compound selected from compounds represented by formulas (1) and (2), and salts of the compounds:

(In formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group. What are R ³ and R ⁴ ? They may be combined with each other to form an alkylidene group, or any two of R ² , R ³ and R ⁴ may be combined with each other to form an alkylene group. Each of these groups has one or more substituents. (It may have a group.)

(In formula (2), R ⁵ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, an amino group, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and R ⁶ is an alkyl group, an aralkyl group. group, aryl group, or heterocyclic group. Each of these groups may have one or more substituents.)
(b) salts (c) chemical blowing agents; and (d) polymeric materials;
A polymer composition containing. A foam obtained by foaming the polymer composition according to claim 4 or 5.