WO2022091599A1 - 発泡ゴム組成物、発泡体及び成形品 - Google Patents

発泡ゴム組成物、発泡体及び成形品 Download PDF

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Publication number
WO2022091599A1
WO2022091599A1 PCT/JP2021/033385 JP2021033385W WO2022091599A1 WO 2022091599 A1 WO2022091599 A1 WO 2022091599A1 JP 2021033385 W JP2021033385 W JP 2021033385W WO 2022091599 A1 WO2022091599 A1 WO 2022091599A1
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Prior art keywords
mass
parts
less
sulfur
compound
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Ceased
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PCT/JP2021/033385
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English (en)
French (fr)
Japanese (ja)
Inventor
敦典 近藤
貴史 砂田
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Denka Co Ltd
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Denka Co Ltd
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Priority to KR1020237012112A priority Critical patent/KR20230095066A/ko
Priority to CN202180068698.9A priority patent/CN116323683A/zh
Priority to EP21885718.3A priority patent/EP4223787A4/en
Priority to JP2022558900A priority patent/JPWO2022091599A1/ja
Priority to US18/249,839 priority patent/US20230383082A1/en
Publication of WO2022091599A1 publication Critical patent/WO2022091599A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/20—Incorporating sulfur atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/22—Incorporating nitrogen atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0033—Use of organic additives containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
    • C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
    • C08L19/003—Precrosslinked rubber; Scrap rubber; Used vulcanised rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2311/00—Characterised by the use of homopolymers or copolymers of chloroprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2319/00—Characterised by the use of rubbers not provided for in groups C08J2307/00 - C08J2317/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

Definitions

  • the present invention relates to a foam rubber composition, a foam, a molded product, and the like.
  • Chloroprene rubber is used as a material for transmission belts or conveyor belts for general industry; air springs for automobiles; anti-vibration rubber, etc., taking advantage of its excellent dynamic properties. Further, it is possible to obtain a chloroprene rubber foam (chloroprene rubber sponge) by mixing chloroprene rubber and a foaming agent and heating and foaming, and the chloroprene rubber foam can be used for automobile parts, construction fields, leisure goods, etc. It is used in various fields of.
  • the foam of chloroprene rubber a foam obtained by mixing an organic peroxide, a foaming agent, a softening agent, a filler and a reinforcing agent with chloroprene rubber and heating and foaming (see, for example, Patent Document 1 below), and , A foam obtained by blending butadiene rubber, a softener and a foaming agent with chloroprene rubber, and foaming by pressureless open vulcanization (see, for example, Patent Document 2 below) is known.
  • the foam of chloroprene rubber is a material having voids, there is a problem that the tear strength is not sufficient.
  • a foam having a high foaming ratio can be obtained, but the tear strength of the foam is small. Therefore, there is a demand for the development of a foam that can be used in applications that require high tear strength (wet suits, etc.).
  • the foam of chloroprene rubber is a material having voids, there is a problem that it shrinks due to aging. Therefore, for a foam rubber composition using chloroprene rubber, there is a demand for the development of a foam rubber composition that gives a foam having high tear strength and a low shrinkage rate.
  • the inventors of the present application have introduced a specific structure at the molecular terminal of the sulfur-modified chloroprene rubber and used a specific amount of a chemical foaming agent to obtain high tear strength and high tear strength.
  • a foamed rubber composition that can obtain a foam having a small shrinkage rate.
  • One aspect of the present invention contains a sulfur-modified chloroprene rubber and a chemical foaming agent, and the sulfur-modified chloroprene rubber has a functional group A represented by the following general formula (A) and located at the molecular terminal, said.
  • the mass ratio B / A of the content of the functional group B represented by the following general formula (B) and located at the end of the molecule to the content of the functional group A is 12.00 or less.
  • the total amount of the functional group A and the functional group B is 0.10 to 1.00% by mass, and the content of the chemical foaming agent is 100 in total of the sulfur-modified chloroprene rubber, the thiazole compound and the dithiocarbamic acid-based compound.
  • a foamed rubber composition which is 3 to 16 parts by mass with respect to parts by mass.
  • R a1 and R a2 independently have a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, a carboxy group, a carboxylic acid base, a cyano group, an alkyl group which may have a substituent, or a substituent.
  • R b1 and R b2 each independently indicate an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • a foam having a high tear strength and a small shrinkage rate can be obtained.
  • Another aspect of the present invention provides a foam of the foam rubber composition described above.
  • Another aspect of the present invention provides a molded product made of the foam.
  • a foamed rubber composition capable of obtaining a foam having a high tear strength and a small shrinkage rate.
  • a foam of the foamed rubber composition it is possible to provide a molded product made of the foam (molded product using the foam).
  • the numerical range indicated by using “-” indicates a range including the numerical values before and after “-" as the minimum value and the maximum value, respectively.
  • “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.
  • 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.
  • 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.
  • 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 "alkyl group” may be linear, branched or cyclic unless otherwise specified.
  • the foamed rubber composition according to the present embodiment contains a sulfur-modified chloroprene rubber and a chemical foaming agent, and the sulfur-modified chloroprene rubber is represented by the following general formula (A) and has a functional group A located at the molecular end (hereinafter referred to as “functional group A”). , "Terminal functional group A”), and in sulfur-modified chloroprene rubber, the functional group B represented by the following general formula (B) and located at the end of the molecule (hereinafter referred to as "terminal functional group B").
  • the mass ratio B / A of the content to the content of the terminal functional group A is 12.00 or less, the total amount of the terminal functional group A and the terminal functional group B is 0.10 to 1.00% by mass, and the chemistry.
  • the content of the foaming agent is 3 to 16 parts by mass with respect to 100 parts by mass of the total of the sulfur-modified chloroprene rubber, the thiazole compound and the dithiocarbamic acid-based compound.
  • R a1 and R a2 independently have a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, a carboxy group, a carboxylic acid base, a cyano group, an alkyl group which may have a substituent, or a substituent. Indicates an arylthio group which may have a substituent.
  • Ra 1 and Ra 2 may be the same as each other or different from each other.
  • R a1 and Ra 2 may be bonded to each other and have a substituent.
  • a good ring may be formed.
  • R a1 and R a2 can be bonded to each other to form a ring having a substituent or a ring having no substituent.
  • R b1 and R b2 each independently represent an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • R b1 and R b2 are the same as each other. However, they may be different from each other.
  • a foam can be obtained by foaming the foamed rubber composition (foamable rubber composition) according to the present embodiment.
  • a foam obtained by foaming the foamed rubber composition a foam having high tear strength and a small shrinkage rate (shrinkage rate of the foam immediately after production) is obtained. It is possible, and in the evaluation of Examples described later, a tear strength of 2.00 N / mm or more (preferably 3.00 N / mm or more or 4.00 N / mm or more) and less than 5.5% (preferably less than 5.5%). Preferably, a shrinkage rate of 5.4% or less or 5.3% or less) can be obtained. Further, according to one aspect of the foamed rubber composition according to the present embodiment, a foam having a high tear strength, a low shrinkage rate, and an excellent appearance can be obtained.
  • Sulfur-modified chloroprene rubber is a polymer having a structural unit derived from chloroprene (2-chloro-1,3-butadiene).
  • the sulfur-modified chloroprene rubber contains a sulfur atom in the molecular chain and may contain a sulfur atom in the main chain.
  • the sulfur-modified chloroprene rubber may contain a polysulfide bond ( S2 to S8 ) in the molecular chain, and may contain a polysulfide bond ( S2 to S8 ) in the main chain.
  • the sulfur-modified chloroprene rubber may have a structural unit derived from a monomer copolymerizable with chloroprene.
  • the monomer copolymerizable with chloroprene include 2,3-dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, styrene, acrylonitrile, methacrylonitrile, isoprene, butadiene, acrylic acid, and methacryl. Examples thereof include acids and these esters.
  • the monomer copolymerizable with chloroprene one type may be used alone, or two or more types may be used in combination.
  • 2,3-dichloro-1,3-butadiene can be used to slow down the crystallization rate of the obtained sulfur-modified chloroprene rubber.
  • Sulfur-modified chloroprene rubber which has a slow crystallization rate, can maintain rubber elasticity even in a low-temperature environment, and can improve, for example, low-temperature compression permanent strain.
  • the amount of the monomer copolymerizable with chloroprene is the total unit containing chloroprene. It is preferably 10% by mass or less in the weight (the total amount of the structural units constituting the sulfur-modified chloroprene rubber). When this amount used is 10% by mass or less, it is easy to suppress a decrease in processability of the obtained sulfur-modified chloroprene rubber.
  • the amount of chloroprene used (content of structural units derived from chloroprene) is 90% by mass or more and 92% by mass in all monomers containing chloroprene (total amount of structural units constituting sulfur-modified chloroprene rubber). % Or more, 95% by mass or more, or 98% by mass or more is preferable.
  • the structural unit constituting the sulfur-modified chloroprene rubber may be a structural unit derived from chloroprene (substantially 100% by mass of the structural unit constituting the sulfur-modified chloroprene rubber is a structural unit derived from chloroprene).
  • the terminal functional group A may be located at the end of the main chain and / or the side chain.
  • the terminal functional group A can be obtained, for example, by using a thiazole compound in the molecular weight adjustment step described later.
  • the substituent for the alkyl group which is R a1 or Ra 2 include a halogen atom, a hydroxy group, an alkoxy group, a carboxy group, a carboxylic acid base, a cyano group, a sulfo group, a sulfonic acid base, a nitro group, an amino group and the like. ..
  • Examples of the substituent for the arylthio group which is R a1 or Ra 2 include an alkyl group, a halogen atom, a hydroxy group, an alkoxy group, a carboxy group, a carboxylic acid base, a cyano group, a sulfo group, a sulfonic acid base, a nitro group and an amino group. Can be mentioned.
  • Ra1 and Ra2 may be bonded to each other to form a ring which may have a substituent.
  • the ring include an aromatic ring, an alicyclic ring, a heterocyclic ring and the like.
  • substituent on the ring include an alkyl group, a halogen atom, a hydroxy group, an alkoxy group, a carboxy group, a carboxylic acid base, a cyano group, a sulfo group, a sulfonic acid base, a nitro group and an amino group.
  • the alkyl group which is a substituent on the ring include an alkyl group having 1, 2, 3 or 4 carbon atoms.
  • the terminal functional group A is a benzothiazole ring formed by bonding Ra1 and Ra2 to each other from the viewpoint that the tear strength is easily improved, the shrinkage rate is easily reduced, and an excellent appearance is easily obtained in the foam. It is preferable to have.
  • the benzothiazole ring does not have to have a substituent.
  • the substituent is preferably an alkyl group from the viewpoints that the tear strength is easily improved, the shrinkage rate is easily reduced, and an excellent appearance is easily obtained in the foam, and the benzothiazole ring is preferable.
  • An alkyl group bonded to the 4-position of is more preferable.
  • the sulfur-modified chloroprene rubber may have a terminal functional group B and may not have a terminal functional group B.
  • the terminal functional group B may be located at the end of the main chain and / or the side chain.
  • the terminal functional group B can be obtained, for example, by using a dithiocarbamic acid-based compound in the molecular weight adjustment step described later.
  • the carbon number of at least one selected from R b1 and R b2 is preferably 6 to 10 from the viewpoints that the tear strength is easily improved, the shrinkage ratio is easily reduced, and an excellent appearance is easily obtained in the foam. -9 is more preferable, and 7-8 is even more preferable.
  • the substituent for the alkyl group which is R b1 or R b2 include a halogen atom, a hydroxy group, an alkoxy group, a carboxy group, a carboxylic acid base, a cyano group, a sulfo group, a sulfonic acid base, a nitro group, an amino group and the like. ..
  • Examples of the aryl group which is R b1 or R b2 include a benzyl group, a phenyl group, a tolyl group, a xsilyl group, a naphthyl group and the like.
  • Examples of the substituent for the aryl group which is R b1 or R b2 include an alkyl group, a halogen atom, a hydroxy group, an alkoxy group, a carboxy group, a carboxylic acid base, a cyano group, a sulfo group, a sulfonic acid base, a nitro group and an amino group. Can be mentioned.
  • the alkyl group or aryl group which is R b1 or R b2 does not have to have a substituent.
  • the foamed rubber composition according to the present embodiment has an embodiment in which the sulfur-modified chloroprene rubber does not have a functional group in which R b1 and R b2 are ethyl groups (unsubstituted ethyl groups) as the terminal functional group B. good.
  • the content of the terminal functional group A is preferably in the following range based on the total amount of the sulfur-modified chloroprene rubber (that is, the sulfur-modified chloroprene rubber has the following numerical value with respect to 100 parts by mass of the sulfur-modified chloroprene rubber (that is, the content of the sulfur-modified chloroprene rubber). Unit: parts by mass) preferably contains the terminal functional group A).
  • the content of the terminal functional group A is 0.50% by mass or less, 0.45% by mass or less, and 0.42% by mass or less from the viewpoint that the tear strength is easily improved and an excellent appearance is easily obtained in the foam.
  • the content of the terminal functional group A is 0.01% by mass or more, 0.03% by mass or more, and 0.04% by mass or more from the viewpoint that the shrinkage rate is easily reduced and an excellent appearance is easily obtained in the foam. , 0.05% by mass or more, 0.06% by mass or more, 0.07% by mass or more, 0.08% by mass or more, 0.09% by mass or more, 0.10% by mass or more, 0.11% by mass or more, 0.12% by mass or more, 0.13% by mass or more, 0.14% by mass or more, 0.15% by mass or more, 0.16% by mass or more, 0.18% by mass or more, 0.20% by mass or more, 0 .23% by mass or more, 0.25% by mass or more, 0.30% by mass or more, 0.35% by mass or more, 0.38% by mass or more, 0.40% by mass or more, or 0.42% by mass or more preferable.
  • the content of the terminal functional group A is 0.01 to 0.50% by mass, 0.04 to 0.42% by mass, 0.04 to 0.40% by mass, 0.04 to 0. 30% by mass, 0.04 to 0.20% by mass, 0.04 to 0.10% by mass, 0.05 to 0.42% by mass, 0.10 to 0.42% by mass, 0.20 to 0. 42% by mass, 0.30 to 0.42% by mass, 0.05 to 0.40% by mass, or 0.08 to 0.30% by mass is preferable.
  • the content of the terminal functional group A can be adjusted by adjusting the amount of the thiazole compound used in the molecular weight adjustment step described later, the treatment time in the molecular weight adjustment step, the treatment temperature, and the like.
  • the content of the terminal functional group B is not particularly limited, but is preferably in the following range based on the total amount of the sulfur-modified chloroprene rubber (that is, the sulfur-modified chloroprene rubber is described below with respect to 100 parts by mass of the sulfur-modified chloroprene rubber. It is preferable to contain the terminal functional group B having a numerical content (unit: parts by mass)).
  • the content of the terminal functional group B is less than 1.00% by mass, 0.90% by mass or less, and 0.80% by mass or less from the viewpoint that the tear strength is easily improved and an excellent appearance is easily obtained in the foam.
  • the content of the terminal functional group B is 0.25% by mass or less, 0.23% by mass or less, and 0.20% by mass or less from the viewpoint that the shrinkage rate is easily reduced and an excellent appearance is easily obtained in the foam.
  • the content of the terminal functional group B may be 0% by mass or more, and may exceed 0% by mass.
  • the content of the terminal functional group B is 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more from the viewpoint that the shrinkage rate is easily reduced and an excellent appearance is easily obtained in the foam.
  • the content of the terminal functional group B is 0.25% by mass or more, 0.29% by mass or more, and 0.30% by mass or more from the viewpoint that the tear strength is easily improved and an excellent appearance is easily obtained in the foam.
  • the content of the terminal functional group B may be 0.50% by mass or more, 0.60% by mass or more, 0.70% by mass or more, or 0.80% by mass or more. From these viewpoints, the content of the terminal functional group B is 0% by mass or more and less than 1.00% by mass, 0 to 0.90% by mass, 0 to 0.80% by mass, 0 to 0.70% by mass, 0.
  • the content of the terminal functional group B can be adjusted by the amount of the dithiocarbamic acid-based compound used in the molecular weight adjustment step described later, the treatment time in the molecular weight adjustment step, the treatment temperature, and the like.
  • the mass ratio B / A of the content of the terminal functional group B to the content of the terminal functional group A is 12.00 or less (0 to 12.00) from the viewpoint of obtaining a small shrinkage rate in the foam.
  • the mass ratio B / A is 11.60 or less, 11.00 or less, 10.00 or less, 9.00 or less, 8.00 or less, 7.00 or less, 6 from the viewpoint that a small shrinkage ratio can be easily obtained in the foam. .00 or less, 5.00 or less, 4.00 or less, 3.00 or less, 2.50 or less, 2.20 or less, 2.00 or less, 1.50 or less, 1.00 or less, 0.60 or less, 0 It may be .50 or less, 0.40 or less, 0.30 or less, 0.20 or less, or 0.10 or less.
  • the mass ratio B / A is 0 or more, and is preferably 0 or more, preferably 0.10 or more, 0.20 or more, 0.30 or more, 0.40 or more from the viewpoint that the tear strength of the foam is easily improved.
  • 0.50 or more, 0.60 or more 1.00 or more, 1.50 or more, 2.00 or more, 2.20 or more, 2.50 or more, 3.00 or more, 4.00 or more, 5.00 or more , 6.00 or more, 7.00 or more, 8.00 or more, 9.00 or more, 10.00 or more, 11.00 or more, or 11.60 or more are preferable.
  • the mass ratio B / A is more than 0 and 12.00 or less, more than 0 and 10.00 or less, more than 0 and 6.00 or less, more than 0 and 1.00 or less, and more than 0 and 0.80.
  • more than 0 and 0.60 or less 0.10 to 12.00, 0.50 to 12.00, 0.55 to 12.00, 0.80 to 12.00, 1.00 to 12.00, 6.00 to 12.00, 8.00 to 12.00, 0.10 to 10.00, 0.50 to 10.00, 1.00 to 10.00, or 1.00 to 6.00 preferable.
  • the total amount of the terminal functional group A and the terminal functional group B (the total content of the terminal functional group A and the terminal functional group B.
  • the total mass (A + B)) is 0.10 to 1 based on the total amount of the sulfur-modified chloroprene rubber. It is 0.00% by mass. If the total mass (A + B) is less than 0.10% by mass, the foam causes an increase in shrinkage and an excellent appearance cannot be obtained. When the total mass (A + B) exceeds 1.00% by mass, the decrease in Mooney viscosity is remarkably impractical (a foam cannot be obtained).
  • the total mass (A + B) may be in the following range based on the total amount of sulfur-modified chloroprene rubber.
  • the total mass (A + B) is 0.15% by mass or more, 0.20% by mass or more, 0.24% by mass or more, and 0.25% by mass or more from the viewpoint of adjusting the balance between tear strength and shrinkage rate in the foam.
  • 0.30% by mass or more 0.35% by mass or more, 0.37% by mass or more, 0.38% by mass or more
  • 0.40% by mass or more 0.42% by mass or more, 0.45% by mass or more, 0.50% by mass or more, 0.51% by mass or more, 0.55% by mass or more, 0.57% by mass or more, 0.60% by mass or more, 0.65% by mass or more, 0.66% by mass or more, 0 It may be .70% by mass or more, 0.80% by mass or more, 0.85% by mass or more, or 0.88% by mass or more.
  • the total mass (A + B) is 0.90% by mass or less, 0.88% by mass or less, 0.85% by mass or less, and 0.80% by mass or less from the viewpoint of adjusting the balance between tear strength and shrinkage rate in the foam. , 0.70% by mass or less, 0.66% by mass or less, 0.65% by mass or less, 0.60% by mass or less, 0.57% by mass or less, 0.55% by mass or less, 0.51% by mass or less, 0.50% by mass or less, 0.45% by mass or less, 0.42% by mass or less, 0.40% by mass or less, 0.38% by mass or less, 0.37% by mass or less, 0.35% by mass or less, 0 It may be .30% by mass or less, 0.25% by mass or less, or 0.24% by mass or less.
  • the total mass (A + B) is 0.20 to 0.90 mass%, 0.20 to 0.70 mass%, 0.20 to 0.65 mass%, 0.20 to 0.55 mass. %, 0.20 to 0.40% by mass, 0.40 to 0.70% by mass, or 0.55 to 0.70% by mass.
  • the content of the terminal functional group A and the terminal functional group B in the sulfur-modified chloroprene rubber can be quantified by the procedure described in the examples.
  • the sulfur-modified chloroprene rubber does not have to have a functional group represented by the following general formula (C), and does not have a functional group represented by the following general formula (C) and located at the molecular terminal. good.
  • R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent.
  • the method for producing sulfur-modified chloroprene rubber includes a polymerization step of emulsion-polymerizing chloroprene in the presence of sulfur ( S8 ) to obtain a polymer, a molecular weight adjustment step (mixing step) of mixing the polymer and a thiazole compound, and a molecular weight adjusting step (mixing step).
  • One aspect of the method for producing sulfur-modified chloroprene rubber is a polymerization step of obtaining a polymerization solution by emulsion polymerization of at least chloroprene and sulfur, and a molecular weight of the polymer in the polymerization solution by adding a thiazole compound to the polymerization solution. It has a molecular weight adjusting step for adjusting the amount of rubber.
  • sulfur can be introduced into a polymer (for example, the main chain of the polymer), and polysulfide bonds ( S2 to S8 ) can also be introduced.
  • Sulfur-modified chloroprene rubber is a sulfur-modified chloroprene polymer in which sulfur is introduced by emulsion polymerization of chloroprene alone or chloroprene and other monomers in the presence of sulfur, and the molecular weight is adjusted using a thiazole compound. Includes the latex obtained from the above and the sulfur-modified chloroprene rubber obtained by drying and washing the latex by a general method.
  • chloroprene is emulsion-polymerized in the presence of sulfur to obtain a polymer.
  • the polymer may be a polymer in a polymerization solution.
  • chloroprene and the above-mentioned monomer copolymerizable with chloroprene may be emulsion-polymerized.
  • the amount of chloroprene used or the amount of the monomer copolymerizable with chloroprene is preferably the above-mentioned amount.
  • the amount of sulfur (S 8 ) used in the emulsion polymerization is preferably in the following range with respect to 100 parts by mass of the monomers (total of the monomers to be polymerized).
  • the amount of sulfur used is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, from the viewpoint that sufficient mechanical properties or dynamic properties of the obtained sulfur-modified chloroprene rubber can be easily obtained.
  • the amount of sulfur used is preferably 0.6 parts by mass or less, preferably 0.5 parts by mass or less, from the viewpoint of easy processing by suppressing the adhesiveness of the obtained sulfur-modified chloroprene rubber to the metal from becoming too strong. Is more preferable. From these viewpoints, the amount of sulfur used is preferably 0.01 to 0.6 parts by mass, more preferably 0.1 to 0.5 parts by mass.
  • emulsifier used for emulsion polymerization one or more known emulsifiers that can be used for emulsion polymerization of chloroprene can be freely selected and used.
  • emulsifiers logoic acids, fatty acids, metal salts of aromatic sulfonic acid formalin condensate, sodium dodecylbenzene sulfonate, potassium dodecylbenzene sulfonate, sodium alkyldiphenyl ether sulfonate, potassium alkyldiphenyl ether sulfonate, polyoxyethylene alkyl ether Examples thereof include sodium sulfonate, sodium polyoxypropylene alkyl ether sulfonate, potassium polyoxyethylene alkyl ether sulfonate, potassium polyoxypropylene alkyl ether sulfonate, and the like.
  • rosin acids are preferable from the viewpoints that the tear strength is easily improved, the shrinkage rate is easily reduced, and an excellent appearance is easily obtained in the foam.
  • the “rosin acids” mean rosin acid, disproportionate rosin acid, alkali metal salts of disproportionate rosin acid (for example, potassium disproportionate rosinate) and the like.
  • the constituent components of the disproportionate rosinic acid include sesquitelpen, 8,5-isopimaric acid, dihydropimaric acid, secodehydroabietic acid, dihydroabietic acid, deisopropyldehydroabietic acid, demethyldehydroabietic acid and the like.
  • fatty acids include fatty acids (for example, saturated or unsaturated fatty acids having 6 to 22 carbon atoms), metal salts of fatty acids (for example, sodium lauryl sulfate) and the like.
  • a metal salt of an aromatic sulfonic acid formalin condensate is preferable, and ⁇ -naphthalene sulfonic acid is preferable from the viewpoint that the tear strength is easily improved, the shrinkage rate is easily reduced, and an excellent appearance is easily obtained in the foam.
  • Sodium salts of formalin condensates are more preferred.
  • the sodium salt of ⁇ -naphthalene sulfonic acid formalin condensate is an emulsifier used for general purposes, and its stability is improved by adding a small amount, and a latex can be stably produced without aggregation and precipitation in the production process. be able to.
  • Other preferably used emulsifiers include, for example, alkaline soap aqueous solutions consisting of a mixture of an alkali metal salt of disproportionate logonic acid and a saturated or unsaturated fatty acid having 6 to 22 carbon atoms.
  • the pH of the emulsion (for example, an aqueous emulsion) at the start of emulsion polymerization is preferably 10.5 or higher.
  • the "emulsifying solution” is a mixed solution of chloroprene and other components (monomer, emulsifier, sulfur ( S8 ), etc. that can be copolymerized with chloroprene) immediately before the start of emulsion polymerization.
  • the "emulsified liquid” also includes cases where the composition thereof is sequentially changed by post-addition, partial addition, etc. of these other components (monomer capable of copolymerizing with chloroprene, sulfur ( S8 ), etc.).
  • the pH of the emulsion When the pH of the emulsion is 10.5 or more, it is possible to prevent polymer precipitation during polymerization and stably control the polymerization. The effect can be particularly preferably obtained when rosin acids are used as the emulsifier.
  • the pH of the emulsion can be adjusted by the amount of alkaline components such as sodium hydroxide and potassium hydroxide present at the time of emulsion polymerization.
  • the polymerization temperature of emulsion polymerization is preferably 0 to 55 ° C, more preferably 30 to 55 ° C, from the viewpoint of excellent polymerization controllability and productivity.
  • the polymerization initiator potassium persulfate, benzoyl peroxide, ammonium persulfate, hydrogen peroxide and the like, which are used in ordinary radical polymerization, can be used.
  • the polymerization is carried out at a polymerization rate (conversion rate) in the following range, and then a polymerization terminator (polymerization inhibitor) is added to terminate the polymerization.
  • the polymerization rate is preferably 60% or more, more preferably 70% or more, from the viewpoint of excellent productivity.
  • the polymerization rate is preferably 95% or less, more preferably 90% or less, from the viewpoint of suppressing the development of a branched structure or gel formation that affects the processability of the obtained sulfur-modified chloroprene rubber. From these viewpoints, the polymerization rate is preferably 60 to 95%, more preferably 70 to 90%.
  • polymerization inhibitor examples include diethylhydroxylamine, thiodiphenylamine, 4-tert-butylcatechol, 2,2'-methylenebis-4-methyl-6-tert-butylphenol and the like.
  • the polymerization inhibitor one type may be used alone, or two or more types may be used in combination.
  • the polymer obtained in the polymerization step and the thiazole compound are mixed.
  • the molecular weight of the polymer can be adjusted by reacting the polymer obtained in the polymerization step and the thiazole compound.
  • the thiazole compound is contained in the polymerization solution obtained in the polymerization step. Can be added to adjust the molecular weight of the polymer in the polymerization solution.
  • sulfur for example, polysulfide bonds ( S2 to S8 )
  • the polymer can be cleaved or depolymerized while forming the terminal functional group A of.
  • the chemical used for cleaving or depolymerizing the polymer is referred to as a "molecular weight adjusting agent".
  • thiazole compound compound having a thiazole ring
  • one or more known thiazole compounds can be freely selected and used.
  • the thiazole compound is N-cyclohexyl-2-benzothiazolesulfenamide, N-cyclohexyl-4- from the viewpoint that the tear strength is easily improved, the shrinkage rate is easily reduced, and an excellent appearance is easily obtained in the foam.
  • the thiazole compound preferably contains a benzothiazole compound (a compound having a benzothiazole ring) from the viewpoint that the tear strength is easily improved, the shrinkage rate is easily reduced, and an excellent appearance is easily obtained in the foam.
  • the foamed rubber composition according to the present embodiment may have an embodiment in which the thiazole compound does not contain N-cyclohexyl-2-benzothiazolesulfenamide and N- (tert-butyl) -2-benzothiazolesulfenamide. ..
  • the amount (addition amount) of the thiazole compound used is preferably 0.2 to 3 parts by mass with respect to 100 parts by mass of the polymer (for example, the polymer in the polymer solution).
  • the amount of the thiazole compound used is 0.2 parts by mass or more, the tear strength is easily improved, the shrinkage rate is easily reduced, and an excellent appearance is easily obtained in the foam.
  • the amount of the thiazole compound used is 3 parts by mass or less, it is easy to obtain an appropriate Mooney viscosity, and as a result, it is easy to improve the vulcanization moldability.
  • the content of the terminal functional group A in the sulfur-modified chloroprene rubber is 0.01 to 0.50% by mass (for example, 0.05 to 0.40% by mass). %. Criteria: The total amount of sulfur-modified chloroprene rubber) can be easily adjusted, and the content (residual amount) of the thiazole compound in the foamed rubber composition is 0.0001 to 0.0200 parts by mass (for example, 0.0005 to 0.0100). By mass. Criteria: 100 parts by mass of sulfur-modified chloroprene rubber) is easy to adjust.
  • a thiazole compound and a dithiocarbamic acid-based compound can be used in combination as the molecular weight adjusting agent.
  • the polymer, thiazole compound, and dithiocarbamic acid-based compound obtained in the polymerization step can be mixed, and the polymer, thiazole compound, and dithiocarbamic acid-based compound obtained in the polymerization step are reacted. Can be made to.
  • the dithiocarbamic acid-based compound reacts with the thiazole compound to form a reactant having higher reactivity with sulfur (for example, polysulfide bond) in the polymer as compared with the case where the thiazole compound alone or the dithiocarbamic acid-based compound alone is used.
  • the Mooney viscosity can be easily adjusted.
  • the reaction product reacts with sulfur in the polymer (for example, a polysulfide bond, for example, sulfur in the main chain of the polymer)
  • the above-mentioned terminal functional group A derived from the thiazole compound and the above-mentioned terminal functional group A derived from the dithiocarbamic acid-based compound are derived.
  • the terminal functional group B of can be suitably formed.
  • dithiocarbamic acid-based compound examples include dithiocarbamic acid, dithiocarbamate, monoalkyldithiocarbamate, monoalkyldithiocarbamate, monoaryldithiocarbamate, monoaryldithiocarbamate, dialkyldithiocarbamate, dialkyldithiocarbamate, diaryldithiocarbamate, and diaryl.
  • dithiocarbamate tetraalkylthiuram disulfide, tetraarylalkylthium disulfide and the like.
  • the salt examples include sodium salt, potassium salt, calcium salt, zinc salt, ammonium salt, nickel salt and the like.
  • the dithiocarbamic acid-based compound one or more known dithiocarbamic acid-based compounds can be freely selected and used.
  • the dithiocarbamic acid-based compound is at least one selected from tetraalkylthiuram disulfide and tetraarylalkylthiuram disulfide from the viewpoints that the tear strength is easily improved, the shrinkage rate is easily reduced, and an excellent appearance is easily obtained in the foam. It preferably contains a compound.
  • Dithiocarbamate-based compounds are dithiocarbamic acid, sodium dithiocarbamate, potassium dithiocarbamate, calcium dithiocarbamate, and dithiocarbamine from the viewpoints that the tear strength is easily improved, the shrinkage rate is easily reduced, and an excellent appearance is easily obtained in the foam.
  • Zinc acid ammonium dithiocarbamate, nickel dithiocarbamate, mono-2-ethylhexyl dithiocarbamate, sodium mono-2-ethylhexyldithiocarbamate, sodium mono-2-ethylhexyldithiocarbamate, calcium mono-2-ethylhexyldithiocarbamate, mono-2- Zinc ethylhexyldithiocarbamate, ammonium mono-2-ethylhexylcarbamate, nickel mono-2-ethylhexylcarbamate, monobenzyldithiocarbamate, sodium monobenzyldithiocarbamate, potassium monobenzyldithiocarbamate, calcium monobenzyldithiocarbamate, monobenzyldithiocarbamate Zinc, ammonium monobenzyldithiocarbamate, nickel monobenzyldithiocarbamate, di-2-ethy
  • the amount (addition amount) of the dithiocarbamic acid-based compound used is not particularly limited, but is preferably 0 to 12 parts by mass, preferably 0 to 8 parts by mass with respect to 100 parts by mass of the polymer (for example, the polymer in the polymer solution). More preferably, it is more preferably more than 0 parts by mass and 8 parts by mass or less, and particularly preferably 0.5 to 4 parts by mass.
  • the amount of the dithiocarbamic acid-based compound used is within these ranges, the Mooney viscosity can be more easily controlled, the tear strength of the foam can be easily improved, and an excellent appearance can be easily obtained.
  • the amount of the dithiocarbamic acid-based compound used is 0 to 12 parts by mass (for example, 0 to 8 parts by mass)
  • the content of the terminal functional group B in the sulfur-modified chloroprene rubber is less than 1.00% by mass (for example, 0.80). It is easy to adjust to mass% or less. Criteria: total amount of sulfur-modified chloroprene rubber), and the content (residual amount) of the dithiocarbamic acid-based compound in the foamed rubber composition is 2.50 parts by mass or less (for example, 2.00 parts by mass or less). Criteria: 100 parts by mass of sulfur-modified chloroprene rubber) is easy to adjust.
  • the polymer solution that has undergone the molecular weight adjustment step may be cooled, pH adjusted, frozen, dried, etc. by a general method to obtain sulfur-modified chloroprene rubber.
  • the foamed rubber composition according to this embodiment contains a chemical foaming agent.
  • the chemical foaming agent may contain at least one selected from organic foaming agents and inorganic foaming agents. Examples of the organic foaming agent include azo compounds, nitroso compounds, sulfonylhydrazide compounds, azide compounds and the like.
  • azo compound examples include azodicarbonamide, azobisformamide, azobisisobutyronitrile, 2,2'-azobisisobutyronitrile, azohexahydrobenzonitrile, diazoaminobenzene and the like.
  • nitroso compound examples include N, N'-dinitrosopentamethylenetetramine, N, N'-dinitroso-N, N'-dimethylphthalamide and the like.
  • Examples of the sulfonyl hydrazide compound include p, p'-oxybisbenzenesulfonyl hydrazide, benzenesulfonyl hydrazide, benzene-1,3-sulfonylhydrazide, diphenylsulfone-3,3'-disulfonylhydrazide, diphenyloxide-4,4'-. Examples thereof include disulfonylhydrazide and paratoluenesulfonylhydrazide.
  • Examples of the azide compound include terephthal azide and pt-butylbenz azide.
  • Examples of the inorganic foaming agent include sodium hydrogen carbonate, ammonium carbonate, sodium bicarbonate, ammonium bicarbonate, ammonium nitrite, calcium azide, sodium azide, sodium borohydride and the like.
  • the chemical foaming agent preferably contains an organic foaming agent from the viewpoints that the tear strength is easily improved, the shrinkage rate is easily reduced, and an excellent appearance is easily obtained in the foam, and an azo compound, a nitroso compound, and a sulfonyl hydrazide are preferable. It is more preferable to contain at least one selected from the compound and the azide compound, and further preferably to contain at least one selected from the azo compound and the sulfonyl hydrazide compound.
  • the chemical foaming agent may contain at least one selected from an azo compound, a nitroso compound, a sulfonylhydrazide compound, an azide compound and an inorganic foaming agent.
  • the decomposition temperature of the chemical foaming agent is preferably 120 to 200 ° C, more preferably 130 to 170 ° C.
  • the decomposition temperature of the chemical foaming agent is within such a range, it is easy to control chemical foaming and vulcanization, and it is easy to reduce the shrinkage rate and obtain an excellent appearance in the foam.
  • the content of the chemical foaming agent is 3 to 16 parts by mass with respect to 100 parts by mass in total of the sulfur-modified chloroprene rubber, the thiazole compound and the dithiocarbamic acid-based compound. If the content of the chemical foaming agent is less than 3 parts by mass, the amount of the foaming agent is insufficient, so that a sufficient amount of decomposition gas may not be obtained to obtain a foam. If the content of the chemical foaming agent exceeds 16 parts by mass, it is difficult to balance foaming and vulcanization, and the appearance or tear strength of the obtained foam may be inferior.
  • the content of the chemical foaming agent is preferably in the following range with respect to a total of 100 parts by mass of the sulfur-modified chloroprene rubber, the thiazole compound and the dithiocarbamic acid-based compound.
  • the content of the chemical foaming agent is 0.1 part by mass or more, 0.5 part by mass or more, from the viewpoint that the tear strength is easily improved, the shrinkage rate is easily reduced, and an excellent appearance is easily obtained in the foam. 1 part by mass or more, 3 parts by mass or more, 4 parts by mass or more, 5 parts by mass or more, 6 parts by mass or more, 6.5 parts by mass or more, 7 parts by mass or more, or 8 parts by mass or more is preferable.
  • the content of the chemical foaming agent is 20 parts by mass or less, 18 parts by mass or less, and 15 parts by mass or less from the viewpoint that the tear strength is easily improved, the shrinkage rate is easily reduced, and an excellent appearance is easily obtained in the foam. , 12 parts by mass or less, 10 parts by mass or less, less than 10 parts by mass, 9 parts by mass or less, or 8 parts by mass or less is preferable.
  • the content of the chemical foaming agent may be 7 parts by mass or less, 6.5 parts by mass or less, 6 parts by mass or less, or 5 parts by mass or less.
  • the content of the chemical foaming agent is 0.1 to 20 parts by mass, 0.1 parts by mass or more and less than 10 parts by mass, 1 to 15 parts by mass, 3 to 15 parts by mass, 5 to 15 parts by mass. 6 to 15 parts by mass, 7 to 15 parts by mass, 8 to 15 parts by mass, 3 to 12 parts by mass, 3 to 10 parts by mass, 3 to 8 parts by mass, 3 to 7 parts by mass, or 3 to 6 parts by mass. preferable.
  • the foamed rubber composition according to the present embodiment may contain an unreacted molecular weight adjusting agent (thiazole compound, dithiocarbamic acid-based compound, etc.).
  • an unreacted molecular weight adjusting agent thiazole compound, dithiocarbamic acid-based compound, etc.
  • the molecular weight adjusting agent the molecular weight adjusting agent described above for the molecular weight adjusting step can be used.
  • the content of the thiazole compound (total amount of the compounds corresponding to the thiazole compound, for example, the residual amount) in the foamed rubber composition according to the present embodiment is preferably in the following range with respect to 100 parts by mass of the sulfur-modified chloroprene rubber.
  • specific thiazole compounds in the foam rubber composition according to the present embodiment for example, each thiazole compound exemplified as described above. N-cyclohexyl-2-benzothiazolesulfenamide, N-cyclohexyl-4-methyl-2-).
  • the content of (benzothiazole sulfenamide, etc.) is preferably in the following range with respect to 100 parts by mass of sulfur-modified chloroprene rubber.
  • the content of the thiazole compound (for example, the residual amount of the unreacted thiazole compound) can be adjusted by the amount of the thiazole compound used in the molecular weight adjustment step, the treatment time in the molecular weight adjustment step, the treatment temperature, and the like.
  • the content of the thiazole compound is 0.0001 parts by mass or more, 0.0003 parts by mass or more, 0.0004 parts by mass or more, 0.0005 parts by mass or more, 0.0006 from the viewpoint that the shrinkage rate is easily reduced in the foam.
  • 0.0010 parts by mass or more 0.0015 parts by mass or more, 0.0020 parts by mass or more, 0.0025 parts by mass or more, 0.0030 parts by mass or more, 0.0031 parts by mass or more, 0.0035 parts by mass Parts or more, 0.0040 parts by mass or more, 0.0045 parts by mass or more, 0.0050 parts by mass or more, 0.0052 parts by mass or more, 0.0055 parts by mass or more, 0.0060 parts by mass or more, 0.0070 parts by mass As mentioned above, 0.0080 parts by mass or more, 0.0090 parts by mass or more, 0.0100 parts by mass or more, or 0.0110 parts by mass or more is preferable.
  • the content of the thiazole compound is 0.0200 parts by mass or less, 0.0150 parts by mass or less, 0.0110 parts by mass or less, 0.0100 parts by mass or less, 0.0090 from the viewpoint that the tear strength is easily improved in the foam.
  • mass or less 0.0080 parts by mass or less, 0.0070 parts by mass or less, 0.0060 parts by mass or less, 0.0055 parts by mass or less, 0.0052 parts by mass or less, 0.0050 parts by mass or less, 0.0045 parts by mass Parts or less, 0.0040 parts by mass or less, 0.0035 parts by mass or less, 0.0031 parts by mass or less, 0.0030 parts by mass or less, 0.0025 parts by mass or less, 0.0020 parts by mass or less, 0.0015 parts by mass
  • it is preferably 0.0010 parts by mass or less, 0.0006 parts by mass or less, 0.0005 parts by mass or less, or 0.0004 parts by mass or less.
  • the content of the thiazole compound is 0.0001 to 0.0200 parts by mass, 0.0004 to 0.0150 parts by mass, 0.0004 to 0.0100 parts by mass, and 0.0004 to 0.0060 parts by mass.
  • Parts, 0.0030 to 0.0100 parts by mass, 0.0050 to 0.0100 parts by mass, or 0.0070 to 0.0100 parts by mass are preferable.
  • the content of the dithiocarbamic acid-based compound (total amount of compounds corresponding to the dithiocarbamic acid-based compound, for example, residual amount) in the foamed rubber composition according to the present embodiment is a viewpoint for adjusting the balance between tear strength and shrinkage rate in the foam. Therefore, the range may be as follows with respect to 100 parts by mass of the sulfur-modified chloroprene rubber.
  • the content of a specific dithiocarbamic acid-based compound for example, each dithiocarbamic acid-based compound exemplified as described above; tetrabenzylthium disulfide, tetrakis (2-ethylhexyl) thiuram disulfide, etc.
  • a specific dithiocarbamic acid-based compound for example, each dithiocarbamic acid-based compound exemplified as described above; tetrabenzylthium disulfide, tetrakis (2-ethylhexyl) thiuram disulfide, etc.
  • the content of the dithiocarbamic acid-based compound (for example, the residual amount of the unreacted dithiocarbamic acid-based compound) can be adjusted by the amount of the dithiocarbamic acid-based compound used in the molecular weight adjustment step, the treatment time in the molecular weight adjustment step, the treatment temperature, and the like.
  • the content of the dithiocarbamic acid-based compound is 2.50 parts by mass or less, 2.00 parts by mass or less, 1.80 parts by mass or less, 1.70 parts by mass or less, 1.50 parts by mass or less, 1.40 parts by mass or less. , 1.37 parts by mass or less, 1.35 parts by mass or less, 1.30 parts by mass or less, 1.20 parts by mass or less, 1.10 parts by mass or less, 1.00 parts by mass or less, 0.90 parts by mass or less, It may be 0.80 parts by mass or less, 0.70 parts by mass or less, 0.60 parts by mass or less, 0.50 parts by mass or less, 0.45 parts by mass or less, or 0.42 parts by mass or less.
  • the content of the dithiocarbamic acid-based compound is 0 parts by mass or more, more than 0 parts by mass, 0.01 parts by mass or more, 0.05 parts by mass or more, 0.10 parts by mass or more, 0.20 parts by mass or more, 0.30.
  • the content of the dithiocarbamic acid-based compound is 0 to 2.50 parts by mass, more than 0 parts by mass and 2.50 parts by mass or less, 0 to 2.00 parts by mass, and more than 0 parts by mass and 2.00.
  • mass or less 0 to 1.70 parts by mass, more than 0 parts by mass and 1.70 parts by mass or less, 0 to 1.35 parts by mass, more than 0 parts by mass and 1.35 parts by mass or less, 0 to 1.00 mass Parts, over 0 parts by mass and below 1.00 parts by mass, 0.40 to 1.70 parts by mass, 0.80 to 1.70 parts by mass, 1.00 to 1.70 parts by mass, 0.40 to 1. It may be 35 parts by mass or 0.40 to 1.00 parts by mass.
  • the mass ratio D / C of the content (for example, residual amount) D of the dithiocarbamic acid-based compound to the content (for example, residual amount) C of the thiazole compound is preferably in the following range.
  • the mass ratio D / C is preferably 2500 or less, 2300 or less, or 2000 or less from the viewpoint of further improving the physical balance between the tear strength and the shrinkage rate of the obtained foam.
  • the mass ratio D / C is 1800 or less, 1600 or less, 1500 or less, 1200 or less, 1000 or less, 800 or less, 700 or less, 600 or less, 500 or less, from the viewpoint of adjusting the balance between tear strength and shrinkage rate in the foam.
  • the mass ratio D / C is 0 or more, and may exceed 0 from the viewpoint of adjusting the balance between tear strength and shrinkage rate in the foam, and may exceed 5 or more, 10 or more, 30 or more, 50 or more, 80 or more, 100. 110 or more, 120 or more, 130 or more, 150 or more, 200 or more, 300 or more, 400 or more, 500 or more, 600 or more, 700 or more, 800 or more, 1000 or more, 1200 or more, 1500 or more, 1600 or more, 1800 or more, Alternatively, it may be 2000 or more.
  • the mass ratio D / C is 0 to 2500, more than 0 and 2500 or less, 0 to 2000, more than 0 and 2000 or less, 0 to 1500, 0 to 1000, 0 to 300, 0 to 130, 100 to. It may be 2500, 130-2500, or 1000-2500.
  • the content of the thiazole compound and the content of the dithiocarbamic acid-based compound can be quantified by the procedure described in the examples.
  • the relative amount of the thiazole compound with respect to the sulfur-modified chloroprene rubber and the relative amount of the dithiocarbamic acid-based compound with respect to the sulfur-modified chloroprene rubber are the sulfur-modified chloroprene rubber and thiazole with respect to the mixture of the sulfur-modified chloroprene rubber, the thiazole compound and the dithiocarbamate-based compound. It can be maintained equally before and after mixing the compound and the components other than the dithiocarbamic acid-based compound.
  • the content of the sulfenamide compound is 0.0005 parts by mass or less, less than 0.0005 parts by mass, and 0.0001 parts by mass with respect to 100 parts by mass of the sulfur-modified chloroprene rubber. It may be less than or equal to 0.00001 parts by mass or less.
  • the foamed rubber composition according to the present embodiment may be substantially free of the sulfenamide compound (the above-mentioned content of the sulfenamide compound may be substantially 0 parts by mass).
  • the content of the organic peroxide is 1 part by mass or less, less than 1 part by mass, 0.1 part by mass or less, or 100 parts by mass with respect to 100 parts by mass of the sulfur-modified chloroprene rubber. It may be 0.01 parts by mass or less.
  • the foamed rubber composition according to the present embodiment does not have to contain substantially an organic peroxide (the above-mentioned content of the organic peroxide may be substantially 0 part by mass).
  • the Mooney viscosity (ML 1 + 4 , 100 ° C.) of the mixture of the sulfur-modified chloroprene rubber, the thiazole compound and the dithiocarbamic acid-based compound is not particularly limited, but the following range is preferable.
  • the Mooney viscosity is preferably 10 or more, 15 or more, 20 or more, 25 or more, or 30 or more from the viewpoint of easily maintaining processability.
  • the Mooney viscosity is preferably 90 or less, 85 or less, 80 or less, 75 or less, 70 or less, 65 or less, 60 or less, 55 or less, or 50 or less from the viewpoint of easily maintaining processability. From these viewpoints, the Mooney viscosity is preferably 10 to 90, or 20 to 80.
  • the Mooney viscosity can be adjusted by the amount of the molecular weight adjusting agent added, the processing time in the molecular weight adjusting step, the processing temperature, and the like.
  • the Mooney viscosity of the mixture of the sulfur-modified chloroprene rubber, the thiazole compound and the dithiocarbamic acid-based compound can be measured by specifying the sulfur-modified chloroprene rubber, the thiazole compound and the dithiocarbamic acid-based compound contained in the foamed rubber composition according to the present embodiment. ..
  • the foamed rubber composition according to the present embodiment may contain additives such as a vulcanizing agent, a processing aid (lubricant), an antiaging agent, a metal compound, a plasticizer, and a filler.
  • additives such as a vulcanizing agent, a processing aid (lubricant), an antiaging agent, a metal compound, a plasticizer, and a filler.
  • the vulcanizing agent examples include metal oxides and the like.
  • the metal oxide include zinc oxide, magnesium oxide, lead oxide, trilead tetraoxide, iron trioxide, titanium dioxide, calcium oxide, hydrotalcite and the like.
  • the vulcanizing agent one type may be used alone, or two or more types may be used in combination.
  • the content of the vulcanizing agent is preferably 3 to 15 parts by mass with respect to 100 parts by mass of the mixture of the sulfur-modified chloroprene rubber, the thiazole compound and the dithiocarbamic acid-based compound.
  • processing aid examples include fatty acids such as stearic acid; paraffin-based processing aids such as polyethylene; fatty acid amides and the like.
  • fatty acids such as stearic acid
  • paraffin-based processing aids such as polyethylene
  • fatty acid amides and the like examples include fatty acids such as stearic acid; paraffin-based processing aids such as polyethylene; fatty acid amides and the like.
  • the content of the processing aid is preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the mixture of the sulfur-modified chloroprene rubber, the thiazole compound and the dithiocarbamic acid-based compound.
  • the foam rubber composition according to the present embodiment can contain an anti-aging agent (for example, a small amount of anti-aging agent) in order to prevent changes in Mooney viscosity during storage.
  • an anti-aging agent for example, a small amount of anti-aging agent
  • one or more known compounds that can be used for chloroprene rubber can be freely selected and used.
  • Anti-aging agents include phenyl- ⁇ -naphthylamine, octylated diphenylamine, nickel dibutyl dithiocarbamate, 2,6-di-tert-butyl-4-phenylphenol, 2,2'-methylenebis (4-methyl-6-tert). -Butylphenol), 4,4'-thiobis- (6-tert-butyl-3-methylphenol) and the like.
  • the anti-aging agent at least one selected from octylated diphenylamine, nickel dibutyl dithiocarbamate and 4,4'-thiobis- (6-tert-but
  • the metal compound suppresses the deterioration of the sulfur-modified chloroprene rubber in order to adjust the vulcanization rate of the sulfur-modified chloroprene rubber or by adsorbing a chlorine source such as hydrogen chloride generated by the dehydrochlorination reaction of the sulfur-modified chloroprene rubber. It is a compound that can be added to the above.
  • oxides such as zinc, titanium, magnesium, lead, iron, beryllium, calcium, barium, germanium, zirconium, vanadium, molybdenum, and tungsten, or hydroxides can be used.
  • the metal compound one kind may be used alone, or two or more kinds may be used in combination.
  • the content of the metal compound is not particularly limited, but is preferably in the range of 3 to 15 parts by mass with respect to 100 parts by mass of the mixture of the sulfur-modified chloroprene rubber, the thiazole compound and the dithiocarbamic acid-based compound. By adjusting the content of the metal compound within this range, the mechanical strength of the molded product can be improved.
  • Plasticizer is a component that can be added to reduce the hardness of sulfur-modified chloroprene rubber and improve its low temperature characteristics. It is also possible to improve the texture of the sponge when producing the sponge using the sulfur-modified chloroprene rubber.
  • the plasticizer include dioctyl phthalate, dioctyl adipate ⁇ also known as bis (2-ethylhexyl) adipate ⁇ , white oil, silicon oil, naphthen oil, aroma oil, triphenyl phosphate, tricresyl phosphate and the like.
  • the plasticizer one type may be used alone, or two or more types may be used in combination.
  • the content of the plasticizer is not particularly limited, but is preferably in the range of 50 parts by mass or less with respect to 100 parts by mass of the mixture of the sulfur-modified chloroprene rubber, the thiazole compound and the dithiocarbamic acid-based compound. By adjusting the content of the plasticizer within this range, the above-mentioned effects of the plasticizer can be exhibited while maintaining the tear strength of the molded product.
  • the filler is a component that can be added as a reinforcing material for sulfur-modified chloroprene rubber.
  • examples of the filler include carbon black, silica, clay, talc, calcium carbonate and the like.
  • the filler one type may be used alone, or two or more types may be used in combination.
  • the foam according to the present embodiment is a foam of the foam rubber composition according to the present embodiment.
  • the foam according to the present embodiment may be a vulcanized product or a sponge.
  • the foam according to the present embodiment can be obtained by foaming the foamed rubber composition according to the present embodiment, and for example, the constituent components of the foamed rubber composition (vulcanized chloroprene rubber, chemical foaming agent, metal). It can be obtained by mixing a compound, a plasticizing agent, a filler, etc.) with a roll, a rubbery mixer, an extruder, or the like, adding a foaming agent, and vulcanizing while foaming.
  • a foam sheet is obtained by slicing the foam according to the present embodiment to a desired thickness, and then a fiber base material (for example, a jersey cloth such as polyester fiber or nylon fiber) is applied to at least one surface of the foam sheet. ) May be laminated (laminated) to obtain a laminated sheet.
  • the laminated sheet according to the present embodiment includes the foam according to the present embodiment and the fiber base material that supports the foam, and the foam is in the form of a sheet.
  • the laminated sheet according to the present embodiment can be used as a fabric for a wet suit, and a wet suit can be obtained by sewing the laminated sheet.
  • the molded product according to the present embodiment is a molded product (for example, a sponge product) made of the foam according to the present embodiment, and can be obtained by molding the foam according to the present embodiment.
  • the molded product include a wet suit and the like.
  • a material having excellent tear strength, shrinkage, appearance and the like is required in order to improve the reliability of the product.
  • the wet suit which is one aspect of the molded product according to the present embodiment, has higher tear strength, lower shrinkage rate, and better appearance than the conventional wet suit using sulfur-modified chloroprene rubber.
  • Example 1 [Making sulfur-modified chloroprene rubber]
  • a polymer can with an internal volume of 30 L, 100 parts by mass of chloroprene, 0.55 parts by mass of sulfur, 120 parts by mass of pure water, 4.00 parts by mass of potassium disproportionate (manufactured by Harima Kasei Co., Ltd.), and 0. 60 parts by mass and 0.6 parts by mass of a sodium salt of ⁇ -naphthalenesulfonic acid formarin condensate (manufactured by Kao Co., Ltd., trade name “Demor N”) were added.
  • the pH of the aqueous emulsion before the start of polymerization was 12.8.
  • Tetrabenzylthium disulfide (molecular weight modifier, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., trade name "Noxeller TBzTD”) 4 parts by mass, sodium salt (dispersant) 0.05 parts by mass of ⁇ -naphthalene sulfonic acid formarin condensate , And 0.05 parts by mass of sodium lauryl sulfate (emulsifying agent) was added to obtain a sulfur-modified chloroprene polymer latex before adjusting the molecular weight.
  • the obtained sulfur-modified chloroprene polymer latex is distilled under reduced pressure to remove unreacted monomers, and then the mixture is kept at a temperature of 50 ° C. for 1 hour with stirring to adjust the molecular weight to contain sulfur-modified chloroprene rubber.
  • Raw rubber (latex after adjusting the molecular weight) was obtained.
  • "Raw rubber” is a mixture containing sulfur-modified chloroprene rubber and an unreacted molecular weight modifier.
  • the content of the terminal functional group in the sulfur-modified chloroprene rubber was quantified by the following procedure. First, the sulfur-modified chloroprene rubber was purified with benzene and methanol, and then freeze-dried again to obtain a sample for measurement. Using this measurement sample, 1 H-NMR measurement was performed according to JIS K-6239. The obtained measurement data was corrected based on the peak of chloroform (7.24 ppm) in deuterated chloroform used as a solvent. Based on the corrected measurement data, the area of each peak having a peak top at 7.72 to 7.83 ppm was calculated to quantify the content of the terminal functional group (thiazole terminal species), and 5.05 to 5.50 ppm. The area of the peak having the peak top was calculated and the content of the terminal functional group (dithiocarbamic acid terminal species) was quantified.
  • the content (residual amount) of the molecular weight adjusting agent with respect to 100 parts by mass of the sulfur-modified chloroprene rubber in the above-mentioned raw rubber was quantified by the following procedure. First, 1.5 g of the obtained raw rubber was dissolved in 30 mL of benzene, and then 60 mL of methanol was added dropwise. As a result, the rubber component (polymer component) was precipitated and separated from the solvent, and the liquid phase containing the non-rubber component as the solvent-soluble component was recovered.
  • the rubber component was separated from the precipitate by dissolving benzene and dropping methanol again in the same procedure, and the liquid phase containing a non-rubber component as a solvent-soluble component was recovered.
  • the volume was adjusted to 200 mL and the obtained liquid was obtained as a measurement sample. 20 ⁇ L of this measurement sample was injected into a liquid chromatograph (LC, manufactured by Hitachi, Ltd., pumps: L-6200, L-600, UV detector: L-4250).
  • the mobile phase of the liquid chromatograph was used with varying proportions of acetonitrile and water and flowed at a flow rate of 1 mL / min.
  • Inertsil ODS-3 ( ⁇ 4.6 ⁇ 150 mm, 5 ⁇ m, manufactured by GL Science Co., Ltd.) was used.
  • the peak detection time was determined using the standard solutions of the thiazole compound (measurement wavelength: 300 nm) of 0.05 ppm, 0.1 ppm and 1.0 ppm and the standard solutions of the dithiocarbamic acid-based compound (measurement wavelength: 280 nm) of 10 ppm, 50 ppm and 100 ppm.
  • the quantitative value was obtained from the calibration curve obtained from the peak area. By comparing this quantitative value with the amount of the sample used for the analysis, the contents of the unreacted thiazole compound and the unreacted dithiocarbamic acid-based compound in the raw rubber were determined.
  • unvulcanized compound (filling rate 105%) is placed in a mold having a cavity region of 100 mm in length, 95 mm in width and 8 mm in height, and the pressure is 3.5 MPa or more and 145 ° C. with respect to the cavity region.
  • Primary vulcanization (first press vulcanization) was performed for 20 minutes. Then, the primary vulcanization compound was obtained by allowing it to stand for 10 minutes under the condition of 23 ° C. under atmospheric pressure.
  • this primary vulcanization compound is placed in a mold having a cavity region of 175 mm in length, 170 mm in width and 16 mm in height, and is secondarily added to the cavity region under the conditions of a pressure of 3.5 MPa or more and 155 ° C. Sulfurization (second press vulcanization) was performed for 20 minutes.
  • Example 2 The amount of N-cyclohexyl-2-benzothiazolesulfenamide added as a molecular weight adjuster was changed from 1 part by mass to 0.5 part by mass, and the amount of tetrabenzylthium disulfide added was changed from 4 parts by mass to 8 parts by mass.
  • An evaluation sample was obtained by the same method as in Example 1 except for the above.
  • Example 3 The amount of N-cyclohexyl-2-benzothiazolesulfenamide added as a molecular weight adjuster was changed from 1 part by mass to 2 parts by mass, and the amount of tetrabenzylthium disulfide added was changed from 4 parts by mass to 2 parts by mass. An evaluation sample was obtained in the same manner as in Example 1 except for the above.
  • Example 4 The amount of N-cyclohexyl-2-benzothiazolesulfenamide added as a molecular weight adjuster was changed from 1 part by mass to 3 parts by mass, and the amount of tetrabenzylthium disulfide added was changed from 4 parts by mass to 2 parts by mass. An evaluation sample was obtained in the same manner as in Example 1 except for the above.
  • Example 5 The amount of N-cyclohexyl-2-benzothiazolesulfenamide added as a molecular weight adjuster was changed from 1 part by mass to 0.5 part by mass, and the amount of tetrabenzylthium disulfide added was changed from 4 parts by mass to 2 parts by mass.
  • An evaluation sample was obtained by the same method as in Example 1 except for the above.
  • Example 6 The same as in Example 1 except that the amount of N-cyclohexyl-2-benzothiazolesulfenamide added as a molecular weight adjusting agent was changed from 1 part by mass to 3 parts by mass and tetrabenzylthiuram disulfide was not added. An evaluation sample was obtained by the method.
  • Example 7 The amount of N-cyclohexyl-2-benzothiazolesulfenamide added as a molecular weight adjuster was changed from 1 part by mass to 0.3 part by mass, and the amount of tetrabenzylthium disulfide added was changed from 4 parts by mass to 8 parts by mass.
  • Raw rubber was obtained in the same manner as in Example 1 except for the above.
  • Example 8 Except for changing the addition amount of N-cyclohexyl-2-benzothiazolesulfenamide, which is a molecular weight adjusting agent, from 1 part by mass to 0.3 part by mass, and changing the treatment time at the time of molecular weight adjustment from 1 hour to 3 hours. Obtained an evaluation sample by the same method as in Example 1.
  • Example 9 Except for changing the addition amount of N-cyclohexyl-2-benzothiazolesulfenamide, which is a molecular weight adjusting agent, from 1 part by mass to 1.5 parts by mass, and changing the treatment time at the time of molecular weight adjustment from 1 hour to 15 minutes. Obtained an evaluation sample by the same method as in Example 1.
  • Example 10 The same method as in Example 1 except that the amount of tetrabenzylthium disulfide added as a molecular weight adjusting agent was changed from 4 parts by mass to 8 parts by mass and the treatment time at the time of adjusting the molecular weight was changed from 1 hour to 15 minutes. A sample for evaluation was obtained at.
  • Example 11 As a molecular weight adjuster, N-cyclohexyl-2-benzothiazolesulfenamide is added to N-cyclohexyl-4-methyl-2-benzothiazolesulfenamide (Chemieliva pharma) which gives a terminal functional group represented by the following formula (A2). & Chem Co., manufactured by LTD), an evaluation sample was obtained by the same method as in Example 1. Based on the total amount of sulfur-modified chloroprene rubber, the content of the terminal functional group (thiazole terminal species A2) derived from N-cyclohexyl-4-methyl-2-benzothiazolesulfenamide is 0.15% by mass, as described above. The content of the terminal functional group (dithiocarbamic acid terminal species B1) derived from tetrabenzylthium disulfide represented by the formula (B1) was 0.33% by mass.
  • Example 12 As a molecular weight adjuster, tetrabenzylthiuram disulfide is used as a tetrakis (2-ethylhexyl) thiuram disulfide (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.), which gives a terminal functional group represented by the following formula (B2), and is traded under the product name "Noxeller TOT-N". An evaluation sample was obtained by the same method as in Example 1 except that it was changed to ").
  • the content of the terminal functional group (thiazole terminal species A1) derived from N-cyclohexyl-2-benzothiazolesulfenamide represented by the above formula (A1) is 0.16 mass.
  • the content of the terminal functional group (dithiocarbamic acid terminal species B2) derived from tetrakis (2-ethylhexyl) thiuram disulfide was 0.25% by mass.
  • Example 13 As a molecular weight adjuster, N-cyclohexyl-2-benzothiazolesulfenamide is changed to N-cyclohexyl-4-methyl-2-benzothiazolesulfenamide which gives a terminal functional group represented by the above formula (A2).
  • A2 N-cyclohexyl-4-methyl-2-benzothiazolesulfenamide
  • B2 tetrabenzylthium disulfide
  • B2 tetrakis (2-ethylhexyl) thiuram disulfide having a terminal functional group represented by the above formula (B2).
  • the content of the terminal functional group (thiazole terminal species A2) derived from N-cyclohexyl-4-methyl-2-benzothiazolesulfenamide is 0.14% by mass, and tetrakis ( The content of the terminal functional group (dithiocarbamic acid terminal species B2) derived from 2-ethylhexyl) thiuram disulfide was 0.32% by mass.
  • Example 14 The same method as in Example 1 except that 8 parts by mass of the foaming agent 1 was changed to 5 parts by mass of the foaming agent 2 (manufactured by Sankyo Kasei Co., Ltd., trade name "Celmic C", azodicarbonamide). An evaluation sample was obtained.
  • Example 15 Except for changing 8 parts by mass of foaming agent 1 to 4 parts by mass of foaming agent 1 and 2.5 parts by mass of foaming agent 2 (manufactured by Sankyo Kasei Co., Ltd., trade name "Celmic C", azodicarbonamide). , An evaluation sample was obtained by the same method as in Example 1.
  • Example 5 An evaluation sample was obtained by the same method as in Example 1 except that the amount of the foaming agent 1 added was changed from 8 parts by mass to 2 parts by mass.
  • Example 6 An evaluation sample was obtained by the same method as in Example 1 except that the amount of the foaming agent 1 added was changed from 8 parts by mass to 20 parts by mass.
  • the Mooney viscosity (ML 1 + 4 ) was measured at a preheating time of 1 minute, a rotation time of 4 minutes, and a test temperature of 100 ° C. of the L-shaped rotor in accordance with JIS K 630-1.
  • the Mooney viscosity of the raw rubber of Comparative Example 1 was too low to measure.
  • the shrinkage ratio is H0 (mm) for the vertical length of the sponge sheet immediately after slicing, L0 (mm) for the horizontal length, H1 (mm) for the vertical length of the sponge sheet after standing for 168 hours, and horizontal.
  • Shrinkage rate (%) [(H0 ⁇ L0-H1 ⁇ L1) ⁇ (H0 ⁇ L0)] ⁇ 100

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