JP2017226829A - Resin composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition capable of obtaining a foamed body which has good moldability at the time of foam molding and is excellent in heat insulation performance.SOLUTION: A resin composition contains (1) a polymer having melting enthalpy observed in a temperature range of 10°C or higher and lower than 60°C by differential scanning calorimetry of 30 J/g or more of 10 wt.% or more and 90 wt.% or less, (2) polystyrene of 10 wt.% or more and 90 wt.% or less, and a copolymer (3) having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound of 0.1 wt.% or more and 50 wt.% or less (where, a total amount of polymer (1), polystyrene (2) and copolymer (3) is 100 wt.%).SELECTED DRAWING: None

Description

  The present invention relates to a novel resin composition containing polystyrene and use thereof.

  Conventionally, polystyrene foam or polyurethane foam has been widely used as a heat insulating material (Patent Document 1, etc.).

JP 59-11227 A

Since the foam has a structure containing gas, it is lightweight and exhibits heat insulation performance. However, the conventional heat insulating material is required to further improve the heat insulating performance.
This invention is made | formed in view of the said subject, The objective is to provide the resin composition from which the moldability at the time of foam molding is good and the foam which is excellent in heat insulation performance is obtained.

（式（１）中、
Ｒは、水素原子またはメチル基を表し、
Ｌ^１は、単結合、―ＣＯ―Ｏ―、―Ｏ―ＣＯ―、または―Ｏ―を表し、
Ｌ^２は、単結合、―ＣＨ_２―、―ＣＨ_２―ＣＨ_２―、―ＣＨ_２―ＣＨ_２―ＣＨ_２―、―ＣＨ_２―ＣＨ（ＯＨ）―ＣＨ_２―、または―ＣＨ_２―ＣＨ（ＣＨ_２ＯＨ）―を表し、
Ｌ^３は、単結合、―ＣＯ―Ｏ―、―Ｏ―ＣＯ―、―Ｏ―、―ＣＯ―ＮＨ―、―ＮＨ―ＣＯ―、―ＣＯ―ＮＨ―ＣＯ―、―ＮＨ―ＣＯ―ＮＨ―、―ＮＨ―、または―Ｎ（ＣＨ_３）―を表し、
Ｌ^６は炭素原子数１４以上３０以下のアルキル基を表し、
Ｌ^１、Ｌ^２、及びＬ^３の化学構造の説明における横書きの化学式の各々は、その左側が式（１）の上側、その右側が式（１）の下側に対応する。）
３） 前記重合体（１）が、エチレンに由来する構成単位（Ａ）と、下記式（１）で示される構成単位（Ｂ）とを有し、さらに下記式（２）で示される構成単位及び下記式（３）で示される構成単位からなる群より選ばれる少なくとも一種の構成単位（Ｃ）とを有してもよく、前記構成単位（Ａ）と前記構成単位（Ｂ）と前記構成単位（Ｃ）の合計数を１００％とするときに、前記構成単位（Ａ）の数が７０％以上９９％以下であり、前記構成単位（Ｂ）と前記構成単位（Ｃ）の合計数が１％以上３０％以下であり、前記構成単位（Ｂ）と前記構成単位（Ｃ）の合計数を１００％とするときに、前記構成単位（Ｂ）の数が１％以上１００％以下であり、前記構成単位（Ｃ）の数が０％以上９９％以下である重合体である１）または２）に記載の樹脂組成物。

（式（１）中、
Ｒは、水素原子またはメチル基を表し、
Ｌ^１は、単結合、―ＣＯ―Ｏ―、―Ｏ―ＣＯ―、または―Ｏ―を表し、
Ｌ^２は、単結合、―ＣＨ_２―、―ＣＨ_２―ＣＨ_２―、―ＣＨ_２―ＣＨ_２―ＣＨ_２―、―ＣＨ_２―ＣＨ（ＯＨ）―ＣＨ_２―、または―ＣＨ_２―ＣＨ（ＣＨ_２ＯＨ）―を表し、
Ｌ^３は、単結合、―ＣＯ―Ｏ―、―Ｏ―ＣＯ―、―Ｏ―、―ＣＯ―ＮＨ―、―ＮＨ―ＣＯ―、―ＣＯ―ＮＨ―ＣＯ―、―ＮＨ―ＣＯ―ＮＨ―、―ＮＨ―、または―Ｎ（ＣＨ_３）―を表し、
Ｌ^６は炭素原子数１４以上３０以下のアルキル基を表し、
Ｌ^１、Ｌ^２、及びＬ^３の化学構造の説明における横書きの化学式の各々は、その左側が式（１）の上側、その右側が式（１）の下側に対応する。）

（式（２）中、
Ｒは、水素原子またはメチル基を表し、
Ｌ^１は、単結合、―ＣＯ―Ｏ―、―Ｏ―ＣＯ―、または―Ｏ―を表し、
Ｌ^４は、炭素原子数１以上８以下のアルキレン基を表し、
Ｌ^５は、水素原子、エポキシ基、―ＣＨ（ＯＨ）―ＣＨ_２ＯＨ、カルボキシ基、ヒドロキシ基、アミノ基、または炭素原子数１以上４以下のアルキルアミノ基を表し、
Ｌ^１の化学構造の説明における横書きの化学式の各々は、その左側が式（２）の上側、その右側が式（２）の下側に対応する。）

４） 前記重合体（１）が、前記構成単位（Ａ）と前記構成単位（Ｂ）と有し、さらに前記構成単位（Ｃ）を有してもよい重合体であって、該重合体に含まれる全ての構成単位の合計数を１００％とするときに、前記構成単位（Ａ）と前記構成単位（Ｂ）と前記構成単位（Ｃ）の合計数が９０％以上である重合体である３）に記載の樹脂組成物。
５） 前記重合体（１）の下記式（Ｉ）で定義される比Ａが０．９５以下である１）〜４）のいずれかに記載の樹脂組成物。
Ａ＝α_１／α_０ （Ｉ）
［式（Ｉ）中、α_１は、
光散乱検出器と粘度検出器を備えた装置を用いるゲル・パーミエイション・クロマトグラフィーにより重合体の絶対分子量と固有粘度を測定し、
絶対分子量の対数を横軸、固有粘度の対数を縦軸として、測定したデータをプロットし、絶対分子量の対数と固有粘度の対数を、横軸が前記重合体の重量平均分子量の対数以上ｚ平均分子量の対数以下の範囲において式（Ｉ−Ｉ）で最小二乗法近似し、式（Ｉ−Ｉ）を表す直線の傾きの値をα_１とすることを含む方法により得られた値である。
ｌｏｇ［η_１］＝α_１ｌｏｇＭ_１＋ｌｏｇＫ_１ （Ｉ−Ｉ）
（式（Ｉ−Ｉ）中、［η_１］は重合体の固有粘度（単位：ｄｌ／ｇ）を表し、Ｍ_１は重合体の絶対分子量を表し、Ｋ_１は定数である。）
式（Ｉ）中、α_０は、
光散乱検出器と粘度検出器を備えた装置を用いるゲル・パーミエイション・クロマトグラフィーによりポリエチレン標準物質１４７５ａ（米国国立標準技術研究所製）の絶対分子量と固有粘度を測定し、
絶対分子量の対数を横軸、固有粘度の対数を縦軸として、測定したデータをプロットし、絶対分子量の対数と固有粘度の対数を、横軸が前記ポリエチレン標準物質１４７５ａの重量平均分子量の対数以上ｚ平均分子量の対数以下の範囲において式（Ｉ−ＩＩ）で最小二乗法近似し、式（Ｉ−ＩＩ）を表す直線の傾きの値をα_０とすることを含む方法により得られた値である。
ｌｏｇ［η_０］＝α_０ｌｏｇＭ_０＋ｌｏｇＫ_０ （Ｉ−ＩＩ）
（式（Ｉ−ＩＩ）中、［η_０］はポリエチレン標準物質１４７５ａの固有粘度（単位：ｄｌ／ｇ）を表し、Ｍ_０はポリエチレン標準物質１４７５ａの絶対分子量を表し、Ｋ_０は定数である。）
なお、ゲル・パーミエイション・クロマトグラフィーによる重合体およびポリエチレン標準物質１４７５ａの絶対分子量と固有粘度の測定において、移動相はオルトジクロロベンゼンであり、測定温度は１５５℃である。］
６） 前記重合体（１）が、架橋されている重合体である１）〜５）のいずれかに記載の樹脂組成物。
７） ゲル分率が２０重量％以上である（ただし、該樹脂組成物の重量を１００重量％とする）、１）〜６）のいずれかに記載の樹脂組成物。
８） 前記共重合体（３）が芳香族ビニル化合物−共役ジエン化合物−芳香族ビニル化合物共重合体の水素添加物である１）〜７）のいずれかに記載の樹脂組成物。
９） １）〜８）のいずれかに記載の樹脂組成物を含む成形体。
１０） １）〜８）のいずれかに記載の樹脂組成物を含む発泡体。 In order to solve the above problems, the present invention provides the following.
1) Polymer (1) having a melting enthalpy of 30 J / g or more observed in a temperature range of 10 ° C. or more and less than 60 ° C. by differential scanning calorimetry, 10% by weight to 90% by weight, polystyrene (2) 10% % To 90% by weight and a copolymer having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound (3) A resin composition comprising 0.1% by weight to 50% by weight (However, the total amount of the polymer (1), polystyrene (2), and copolymer (3) is 100% by weight).
2) The resin composition according to 1), wherein the polymer (1) is a polymer having a structural unit (B) represented by the following formula (1).

(In the formula (1),
R represents a hydrogen atom or a methyl group,
L ¹ represents a single bond, —CO—O—, —O—CO—, or —O—,
L ² represents a single _{bond, -CH 2 -, - CH 2} -CH 2 -, - CH 2 -CH 2 -CH 2 -, - CH 2 -CH (OH) -CH 2 -, or _-CH 2 -CH (CH ₂ OH) —
L ³ is a single bond, —CO—O—, —O—CO—, —O—, —CO—NH—, —NH—CO—, —CO—NH—CO—, —NH—CO—NH—. , -NH-, or -N (CH ₃ )-
L ⁶ represents an alkyl group having 14 to 30 carbon atoms,
Each of the horizontal chemical formulas in the description of the chemical structures of L ¹ , L ² , and L ³ corresponds to the upper side of the formula (1) on the left side and the lower side of the formula (1) on the right side. )
3) The polymer (1) has a structural unit (A) derived from ethylene and a structural unit (B) represented by the following formula (1), and further represented by the following formula (2). And at least one structural unit (C) selected from the group consisting of structural units represented by the following formula (3), the structural unit (A), the structural unit (B), and the structural unit When the total number of (C) is 100%, the number of the structural units (A) is 70% or more and 99% or less, and the total number of the structural units (B) and the structural units (C) is 1. % To 30%, and when the total number of the structural unit (B) and the structural unit (C) is 100%, the number of the structural units (B) is 1% to 100%, The polymer according to 1) or 2), wherein the number of the structural units (C) is from 0% to 99%. Resin composition.

(In the formula (1),
R represents a hydrogen atom or a methyl group,
L ¹ represents a single bond, —CO—O—, —O—CO—, or —O—,
L ² represents a single _{bond, -CH 2 -, - CH 2} -CH 2 -, - CH 2 -CH 2 -CH 2 -, - CH 2 -CH (OH) -CH 2 -, or _-CH 2 -CH (CH ₂ OH) —
L ³ is a single bond, —CO—O—, —O—CO—, —O—, —CO—NH—, —NH—CO—, —CO—NH—CO—, —NH—CO—NH—. , -NH-, or -N (CH ₃ )-
L ⁶ represents an alkyl group having 14 to 30 carbon atoms,
Each of the horizontal chemical formulas in the description of the chemical structures of L ¹ , L ² , and L ³ corresponds to the upper side of the formula (1) on the left side and the lower side of the formula (1) on the right side. )

(In the formula (2),
R represents a hydrogen atom or a methyl group,
L ¹ represents a single bond, —CO—O—, —O—CO—, or —O—,
L ⁴ represents an alkylene group having 1 to 8 carbon atoms,
L ⁵ represents a hydrogen atom, an epoxy group, —CH (OH) —CH ₂ OH, a carboxy group, a hydroxy group, an amino group, or an alkylamino group having 1 to 4 carbon atoms,
Each of the horizontal chemical formulas in the description of the chemical structure of L ¹ corresponds to the upper side of the formula (2) on the left side and the lower side of the formula (2) on the right side. )

4) The polymer (1) includes the structural unit (A) and the structural unit (B), and may further include the structural unit (C). A polymer in which the total number of the structural units (A), the structural units (B), and the structural units (C) is 90% or more when the total number of all the structural units included is 100%. The resin composition as described in 3).
5) The resin composition according to any one of 1) to 4), wherein the ratio A defined by the following formula (I) of the polymer (1) is 0.95 or less.
A = α ₁ / α ₀ (I)
[In the formula (I), α ₁ is
Measure the absolute molecular weight and intrinsic viscosity of the polymer by gel permeation chromatography using a device with a light scattering detector and a viscosity detector,
The measured data is plotted with the logarithm of the absolute molecular weight as the horizontal axis and the logarithm of the intrinsic viscosity as the vertical axis. This is a value obtained by a method including approximation by the least squares method with the formula (II) in a range equal to or lower than the logarithm of the molecular weight and setting the value of the slope of the straight line representing the formula (II) as α ₁ .
log [η ₁ ] = α ₁ logM ₁ + logK ₁ (I−I)
(In formula (II), [η ₁ ] represents the intrinsic viscosity (unit: dl / g) of the polymer, M ₁ represents the absolute molecular weight of the polymer, and K ₁ is a constant.)
In the formula (I), α ₀ is
The absolute molecular weight and intrinsic viscosity of polyethylene standard substance 1475a (manufactured by National Institute of Standards and Technology) are measured by gel permeation chromatography using a device equipped with a light scattering detector and a viscosity detector.
The measured data is plotted with the logarithm of absolute molecular weight as the horizontal axis and the logarithm of intrinsic viscosity as the vertical axis. in logarithmic the range of z-average molecular weight approximating the minimum square method by the formula (I-II), a value obtained by a process comprising the value of the slope of the straight line representing the formula (I-II) and alpha ₀ is there.
log [η ₀ ] = α ₀ logM ₀ + log K ₀ (I-II)
(In the formula (I-II), [η ₀ ] represents the intrinsic viscosity (unit: dl / g) of the polyethylene standard material 1475a, M ₀ represents the absolute molecular weight of the polyethylene standard material 1475a, and K ₀ is a constant. .)
In the measurement of the absolute molecular weight and intrinsic viscosity of the polymer and polyethylene standard substance 1475a by gel permeation chromatography, the mobile phase is orthodichlorobenzene and the measurement temperature is 155 ° C. ]
6) The resin composition according to any one of 1) to 5), wherein the polymer (1) is a crosslinked polymer.
7) The resin composition according to any one of 1) to 6), wherein the gel fraction is 20% by weight or more (provided that the weight of the resin composition is 100% by weight).
8) The resin composition according to any one of 1) to 7), wherein the copolymer (3) is a hydrogenated product of an aromatic vinyl compound-conjugated diene compound-aromatic vinyl compound copolymer.
9) A molded article comprising the resin composition according to any one of 1) to 8).
10) A foam comprising the resin composition according to any one of 1) to 8).

  ADVANTAGE OF THE INVENTION According to this invention, the moldability at the time of foam molding is good, and the resin composition from which the foam excellent in heat insulation performance is obtained can be provided.

<Polymer (1)>
The polymer (1) contained in the resin composition of the present invention is a polymer having a melting enthalpy of 30 J / g or more observed in a temperature range of 10 ° C. or more and less than 60 ° C. by differential scanning calorimetry. In the following, the melting enthalpy may be expressed as ΔH. ΔH observed in the temperature range of 10 ° C. or more and less than 60 ° C. of the polymer (1) is preferably 50 J / g or more, more preferably 70 J / g or more. Moreover, (DELTA) H of a polymer (1) is 200 J / g or less normally.

In the present specification, “melting enthalpy” means that a portion within a temperature range of 10 ° C. or more and less than 60 ° C. of a melting curve measured by the following differential scanning calorimetry is analyzed by a method according to JIS K7122-1987. This is the heat of fusion obtained. By adjusting the number of the following structural units (B) in the polymer (1) and the number of carbon atoms of L ⁶ in the following formula (1) of the following structural units (B), the ΔH is adjusted to the above range. Can be inside.
[Differential scanning calorimetry]
With a differential scanning calorimeter, an aluminum pan encapsulating about 5 mg of sample in a nitrogen atmosphere was (1) held at 150 ° C. for 5 minutes, then (2) from 150 ° C. to −50 at a rate of 5 ° C./min. Then, the temperature is lowered to (3) -50 ° C for 5 minutes, and (4) the temperature is raised from -50 ° C to 150 ° C at a rate of 5 ° C / min. The differential scanning calorimetry curve obtained by calorimetry in step (4) is taken as the melting curve.

The melting peak temperature of the polymer (1) is preferably 10 ° C. or higher and 60 ° C. or lower.
In this specification, the melting peak temperature of the polymer is the temperature at the top of the melting peak obtained by analyzing the melting curve measured by the differential scanning calorimetry by a method according to JIS K7121-1987, This is the temperature at which the melting endotherm becomes maximum. When there are a plurality of melting peaks defined by JIS K7121-1987 in the melting curve, the temperature at the top of the melting peak having the maximum melting endotherm is defined as the melting peak temperature.
By adjusting the number of the following structural units (B) in the polymer (1) and the number of carbon atoms of L ⁶ in the following formula (1) of the following structural units (B), the polymer (1) The melting peak temperature of can be adjusted. As a result, the heat storage performance of the resin composition containing the polymer (1) can be adjusted.

  One embodiment of the polymer (1) includes a polymer containing a structural unit having an alkyl group having 14 to 30 carbon atoms.

（式（１）中、
Ｒは水素原子またはメチル基を表し、
Ｌ^１は、単結合、―ＣＯ―Ｏ―、―Ｏ―ＣＯ―、または―Ｏ―を表し、
Ｌ^２は、単結合、―ＣＨ_２―、―ＣＨ_２―ＣＨ_２―、―ＣＨ_２―ＣＨ_２―ＣＨ_２―、―ＣＨ_２―ＣＨ（ＯＨ）―ＣＨ_２―、または―ＣＨ_２―ＣＨ（ＣＨ_２ＯＨ）―を表し、
Ｌ^３は、単結合、―ＣＯ―Ｏ―、―Ｏ―ＣＯ―、―Ｏ―、―ＣＯ―ＮＨ―、―ＮＨ―ＣＯ―、―ＣＯ―ＮＨ―ＣＯ―、―ＮＨ―ＣＯ―ＮＨ―、―ＮＨ―、または―Ｎ（ＣＨ_３）―を表し、
Ｌ^６は炭素原子数１４以上３０以下のアルキル基を表す。）
（なお、Ｌ^１、Ｌ^２、及びＬ^３の化学構造の説明における横書きの化学式の各々は、その左側が式（１）の上側、その右側が式（１）の下側に対応する。） The polymer (1) is preferably a polymer having a structural unit (B) represented by the following formula (1).

(In the formula (1),
R represents a hydrogen atom or a methyl group,
L ¹ represents a single bond, —CO—O—, —O—CO—, or —O—,
L ² represents a single _{bond, -CH 2 -, - CH 2} -CH 2 -, - CH 2 -CH 2 -CH 2 -, - CH 2 -CH (OH) -CH 2 -, or _-CH 2 -CH (CH ₂ OH) —
L ³ is a single bond, —CO—O—, —O—CO—, —O—, —CO—NH—, —NH—CO—, —CO—NH—CO—, —NH—CO—NH—. , -NH-, or -N (CH ₃ )-
L ⁶ represents an alkyl group having 14 to 30 carbon atoms. )
(In each of the horizontal chemical formulas in the description of the chemical structures of L ¹ , L ² , and L ³ , the left side corresponds to the upper side of formula (1) and the right side corresponds to the lower side of formula (1).)

  R is preferably a hydrogen atom.

L ¹ is preferably —CO—O—, —O—CO—, or —O—, more preferably —CO—O— or —O—CO—, and still more preferably —CO—. O-.

L ² is preferably a single _{bond, -CH 2 -, - CH 2} -CH 2 -, or _-CH 2 _-CH 2 -CH ₂ -, more preferably an a single bond.

L ³ is preferably a single bond, —O—CO—, —O—, —NH—, or —N (CH ₃ ) —, and more preferably a single bond.

L ⁶ in Formula (1) is an alkyl group having 14 to 30 carbon atoms so that the moldability of the polymer composition (1) and the resin composition containing the polymer (1) is good. . Examples of the alkyl group having 14 to 30 carbon atoms include a linear alkyl group having 14 to 30 carbon atoms and a branched alkyl group having 14 to 30 carbon atoms. L ⁶ is preferably a linear alkyl group having 14 to 30 carbon atoms, more preferably a linear alkyl group having 14 to 24 carbon atoms, and still more preferably 16 to 22 carbon atoms. A linear alkyl group.

  Examples of the linear alkyl group having 14 to 30 carbon atoms include n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-eicosyl. Group, n-heneicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group, and n- A triacontyl group may be mentioned.

  Examples of the branched alkyl group having 14 to 30 carbon atoms include isotetradecyl group, isopentadecyl group, isohexadecyl group, isoheptadecyl group, isooctadecyl group, isononadecyl group, isoeicosyl group, isoheneicosyl group, Examples thereof include an isodocosyl group, an isotricosyl group, an isotetracosyl group, an isopentacosyl group, an isohexacosyl group, an isoheptacosyl group, an isooctacosyl group, an isononacosyl group, and an isotriacontyl group.

Examples of the combination of R, L ¹ , L ² and L ³ in formula (1) include the following.

The combination of R, L ¹ , L ² and L ³ in formula (1) is preferably as follows.

As the combination of R, L ¹ , L ² and L ³ in the formula (1), the following are also preferable. R is a hydrogen atom, L ¹ , L ² , and L ³ are single bonds, and L ⁶ is an alkyl group having 14 to 30 carbon atoms,
R is a hydrogen atom or a methyl group, L ¹ is —CO—O—, L ² and L ³ are single bonds, and L ⁶ is an alkyl group having 14 to 30 carbon atoms.

The combination of R, L ¹ , L ² and L ³ in the formula (1) is more preferably as follows.

The combination of R, L ¹ , L ² and L ³ in the formula (1) is more preferably as follows.

  The structural unit (B) is preferably a structural unit derived from n-hexadecene, a structural unit derived from n-octadecene, a structural unit derived from n-eicosene, a structural unit derived from n-docosene, or n-tetracocene. , A structural unit derived from n-hexacocene, a structural unit derived from n-octacosene, a structural unit derived from n-triacontane, a structural unit derived from n-detriacontene, n-tetradecyl acrylate A structural unit derived from n, a structural unit derived from n-pentadecyl acrylate, a structural unit derived from n-hexadecyl acrylate, a structural unit derived from n-heptadecyl acrylate, a structural unit derived from n-octadecyl acrylate, n A structural unit derived from nonadecyl acrylate, n-eicosyl acrylate Derived from n-heneicosyl acrylate, derived from n-docosyl acrylate, derived from n-tricosyl acrylate, derived from n-tetracosyl acrylate Structural unit, structural unit derived from n-pentacosyl acrylate, structural unit derived from n-hexacosyl acrylate, structural unit derived from n-heptacosyl acrylate, structural unit derived from n-octacosyl acrylate , A structural unit derived from n-nonacosyl acrylate, a structural unit derived from n-triacontyl acrylate, a structural unit derived from n-tetradecyl methacrylate, a structural unit derived from n-pentadecyl methacrylate, n-hexadecyl Structural unit derived from methacrylate, n-heptadecyl Structural unit derived from tacrylate, structural unit derived from n-octadecyl methacrylate, structural unit derived from n-nonadecyl methacrylate, structural unit derived from n-eicosyl methacrylate, structural unit derived from n-heneicosyl methacrylate , A structural unit derived from n-docosyl methacrylate, a structural unit derived from n-tricosyl methacrylate, a structural unit derived from n-tetracosyl methacrylate, a structural unit derived from n-pentacosyl methacrylate, n-hexa Structural units derived from cosyl methacrylate, structural units derived from n-heptacosyl methacrylate, structural units derived from n-octacosyl methacrylate, structural units derived from n-nonacosyl methacrylate, n-triacontyl methacrylate Structure derived from Structural unit, structural unit derived from n-vinyltetradecylate, structural unit derived from n-vinylhexadecylate, structural unit derived from n-vinyloctadecylate, structural unit derived from n-vinyleicosylate , A structural unit derived from n-vinyl docosylate, a structural unit derived from n-tetradecyl vinyl ether, a structural unit derived from n-hexadecyl vinyl ether, a structural unit derived from n-octadecyl vinyl ether, n-eicosyl vinyl ether Or a structural unit derived from n-docosyl vinyl ether.

  The polymer (1) may have two or more kinds of the structural unit (B), for example, a structural unit derived from n-eicosyl acrylate, and a structural unit derived from n-octadecyl acrylate. It may be a polymer having

The polymer (1) includes a shape-retaining property of a molded article comprising the resin composition containing the polymer (1) at a melting peak temperature or higher of the polymer (1), and the polymer (1). It is preferable that it is a polymer which has the structural unit (A) derived from ethylene so that the moldability of the resin composition containing this may be favorable. The structural unit (A) is a structural unit formed by polymerizing ethylene, and the structural unit (A) may form a branched structure in the polymer.
The polymer (1) is preferably a polymer having the structural unit (B) represented by the formula (1) and the structural unit (A) derived from ethylene.

（式（２）中、
Ｒは、水素原子またはメチル基を表し、
Ｌ^１は、単結合、―ＣＯ―Ｏ―、―Ｏ―ＣＯ―、または―Ｏ―を表し、
Ｌ^４は、炭素原子数１以上８以下のアルキレン基を表し、
Ｌ^５は、水素原子、エポキシ基、―ＣＨ（ＯＨ）―ＣＨ_２ＯＨ、カルボキシ基、ヒドロキシ基、アミノ基、または炭素原子数１以上４以下のアルキルアミノ基を表す。）
（なお、Ｌ^１の化学構造の説明における横書きの化学式の各々は、その左側が式（２）の上側、その右側が式（２）の下側に対応する。）

The polymer (1) may have at least one structural unit (C) selected from the group consisting of a structural unit represented by the following formula (2) and a structural unit represented by the following formula (3). .

(In the formula (2),
R represents a hydrogen atom or a methyl group,
L ¹ represents a single bond, —CO—O—, —O—CO—, or —O—,
L ⁴ represents an alkylene group having 1 to 8 carbon atoms,
L ⁵ represents a hydrogen atom, an epoxy group, —CH (OH) —CH ₂ OH, a carboxy group, a hydroxy group, an amino group, or an alkylamino group having 1 to 4 carbon atoms. )
(In each of the horizontal chemical formulas in the description of the chemical structure of L ¹ , the left side corresponds to the upper side of formula (2), and the right side corresponds to the lower side of formula (2).)

  In the formula (2), R is preferably a hydrogen atom.

In the formula (2), L ¹ is preferably —CO—O—, —O—CO—, or —O—, more preferably —CO—O— or —O—CO—, Preferably, -CO-O-.

In formula (2), examples of the alkylene group having 1 to 8 carbon atoms as L ⁴ include methylene group, ethylene group, n-propylene group, 1-methylethylene group, n-butylene group, 1,2 -Dimethylethylene group, 1,1-dimethylethylene group, 2,2-dimethylethylene group, n-pentylene group, n-hexylene group, n-heptalene group, n-octylene group, and 2-ethyl-n- A xylene group may be mentioned.

L ⁴ is preferably a methylene group, an ethylene group, and an n-propylene group, and more preferably a methylene group.

In the formula (2), examples of the alkylamino group having 1 to 4 carbon atoms as L ⁵ include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a dimethylamino group, and a diethylamino group. Can be mentioned.

In the formula (2), L ⁵ is preferably a hydrogen atom, an epoxy group, or —CH (OH) —CH ₂ OH, more preferably a hydrogen atom.

Examples of the combination of R, L ¹ , L ⁴ and L ⁵ in formula (2) include the following.

The combination of R, L ¹ , L ⁴ and L ⁵ in formula (2) is preferably as follows.

The combination of R, L ¹ , L ⁴ and L ⁵ in formula (2) is more preferably as follows.

The combination of R, L ¹ , L ⁴ and L ⁵ in formula (2) is more preferably as follows.

Examples of the structural unit represented by the formula (2) include a structural unit derived from propylene, a structural unit derived from butene, a structural unit derived from 1-pentene, a structural unit derived from 1-hexene, and 1-heptene. Structural unit derived, structural unit derived from 1-octene, structural unit derived from acrylic acid, structural unit derived from methacrylic acid, structural unit derived from vinyl alcohol, structural unit derived from methyl acrylate, derived from ethyl acrylate A structural unit derived from n-propyl acrylate, a structural unit derived from isopropyl acrylate, a structural unit derived from n-butyl acrylate, a structural unit derived from isobutyl acrylate, a structural unit derived from sec-butyl acrylate, Structural units derived from tert-butyl acrylate Structural units derived from methyl methacrylate, structural units derived from ethyl methacrylate, structural units derived from n-propyl methacrylate, structural units derived from isopropyl methacrylate, structural units derived from n-butyl methacrylate, structures derived from isobutyl methacrylate Units, structural units derived from sec-butyl methacrylate, structural units derived from tert-butyl methacrylate, structural units derived from vinyl formate, structural units derived from vinyl acetate, structural units derived from vinyl propionate, vinyl Structural units derived from (n-butyrate), structural units derived from vinyl (isobutyrate), structural units derived from methyl vinyl ether, structural units derived from ethyl vinyl ether, n-propyl vinyl ether Structural unit derived, structural unit derived from isopropyl vinyl ether, structural unit derived from n-butyl vinyl ether, structural unit derived from isobutyl vinyl ether, structural unit derived from sec-butyl vinyl ether, structural unit derived from tert-butyl vinyl ether , A structural unit derived from glycidyl acrylate, a structural unit derived from glycidyl methacrylate, a structural unit derived from 2,3-dihydroxypropyl acrylate, a structural unit derived from 2,3-dihydroxypropyl methacrylate, 3- (dimethylamino) propyl Examples include a structural unit derived from acrylate and a structural unit derived from 3- (dimethylamino) propyl methacrylate.
The structural unit represented by the formula (3) is a structural unit derived from maleic anhydride.

  The polymer (1) may have two or more kinds of the structural unit (C), for example, a structural unit derived from methyl acrylate, a structural unit derived from ethyl acrylate, and a glycidyl methacrylate. It may be a polymer having a structural unit.

The polymer (1) is preferably a polymer having the structural unit (B) represented by the formula (1).
As the polymer having the structural unit (B) represented by the formula (1),
A polymer (1) comprising the structural unit (B),
A polymer (1) having the structural unit (B) and the structural unit (A),
The polymer (1) having the structural unit (B) and the structural unit (C), and the polymer (1) having the structural unit (B), the structural unit (A), and the structural unit (C). )
Is mentioned.

As the polymer (1) comprising the structural unit (B),
From the structural unit (B) represented by the formula (1), wherein R is a hydrogen atom, L ¹ , L ² , and L ³ are single bonds, and L ⁶ is an alkyl group having 14 to 30 carbon atoms. A polymer, and
In the formula (1), R is a hydrogen atom or a methyl group, L ¹ is —CO—O—, L ² and L ³ are single bonds, and L ⁶ is an alkyl group having 14 to 30 carbon atoms. The polymer which consists of a structural unit (B) shown is mentioned.

As the polymer (1) having the structural unit (B) and the structural unit (A),
A structural unit (B) represented by formula (1) wherein R is a hydrogen atom, L ¹ , L ² , and L ³ are single bonds, and L ⁶ is an alkyl group having 14 to 30 carbon atoms; And when the total number of all structural units contained in the polymer is 100%, the total number of the structural units (A) and the structural units (B) is A polymer that is 90% or more, and R is a hydrogen atom or a methyl group, L ¹ is —CO—O—, L ² and L ³ are single bonds, and L ⁶ is 14 to 30 carbon atoms. A polymer having the structural unit (B) represented by the following formula (1), which is an alkyl group, and the structural unit (A), and further having the structural unit (C), When the total number of all the structural units contained in the polymer is 100%, the structural unit (A) and the structural unit The total number of units (B) can be mentioned a polymer of 90% or more.

  From the viewpoint of increasing ΔH, when the total number of the structural units (B) and the structural units (A) contained in the polymer is 100%, the polymer (1) A polymer in which the number of B) is more than 50% and 80% or less is preferred.

  From the viewpoint of molding processability, the polymer (1) has the structural unit (B) when the total number of the structural unit (B) and the structural unit (A) contained in the polymer is 100%. ) Is preferably 10% or more and 50% or less.

As the polymer (1) having the structural unit (B) and the structural unit (C),
Formula (1) wherein R is a hydrogen atom or a methyl group, L ¹ is —CO—O—, L ² and L ³ are single bonds, and L ⁶ is an alkyl group having 14 to 30 carbon atoms. And a structural unit (B) represented by formula (2), wherein R is a hydrogen atom or a methyl group, L ¹ is —CO—O—, L ⁴ is a methylene group, and L ⁵ is a hydrogen atom. And a polymer having a structural unit (C) represented by In this case, when the total number of the structural unit (B) and the structural unit (C) contained in the polymer is 100%, a polymer in which the number of the structural units (B) is 80% or more is obtained. preferable.

In the polymer (1), when the total number of the structural unit (A), the structural unit (B), and the structural unit (C) is 100%, the number of the structural units (A) is 0%. 99% or less, the total number of the structural unit (B) and the structural unit (C) is 1% or more and 100% or less, and the total number of the structural unit (B) and the structural unit (C) is When 100%, the number of the structural units (B) is 1% or more and 100% or less, and the number of the structural units (C) is 0% or more and 99% or less.
The number of the structural units (A) in the polymer (1) is determined when the total number of the structural units (A), the structural units (B), and the structural units (C) is 100%. In order that the shape-retaining property of the molded product containing the resin composition is good, it is preferably 70% or more and 99% or less, more preferably 80% or more and 97.5% or less, and still more preferably 85%. It is 92.5% or less. The total number of the structural unit (B) and the structural unit (C) in the polymer (1) is 100 as the total number of the structural unit (A), the structural unit (B), and the structural unit (C). %, Preferably 1% or more and 30% or less, and more preferably 2.5% or more and 20% or less so that the shape-retaining property of the molded article containing the resin composition according to the present invention is good. More preferably, it is 7.5% or more and 15% or less.
The number of the structural unit (B) in the polymer (1) is 1% or more and 100% or less when the total number of the structural unit (B) and the structural unit (C) is 100%. It is preferably 60% or more and 100% or less, and more preferably 80% or more and 100% or less so that the heat storage performance of the resin composition containing the polymer (1) is good. The number of the structural units (C) in the polymer (1) is 0% or more and 99% or less when the total number of the structural units (B) and the structural units (C) is 100%. It is preferably 0% or more and 40% or less, and more preferably 0% or more and 20% or less so that the heat storage performance of the resin composition containing the polymer (1) is good.

The number of the structural unit (A), the number of the structural unit (B), and the number of the structural unit (C) are determined according to a known method by ¹³ C nuclear magnetic resonance spectrum (hereinafter, ¹³ C-NMR spectrum) or ¹ It is calculated | required from the integral value of the signal which belongs to each structural unit of H nuclear magnetic resonance spectrum (henceforth, < ¹ > H-NMR spectrum).
As described later, the polymer (1) has at least one structural unit (C) selected from the group consisting of the structural unit represented by the above formula (2) and the structural unit represented by the above formula (3). And a polymer that may have a structural unit (A) derived from ethylene (hereinafter referred to as precursor polymer (1)) and at least one compound (α) described later. The number of the structural unit (A), the number of the structural unit (B), and the number of the structural unit (C) can be determined by the following method, for example.
When the precursor polymer (1) includes a structural unit (A) derived from ethylene, first, the number of the structural unit (A) and the structural unit (C) included in the precursor polymer (1) is obtained. ^When obtaining from a ¹³ C-NMR spectrum, for example, the number of dyads (AA, AC, CC) of the structural unit (A) and the structural unit (C) is determined from the spectrum, and substituted into the following formula, The number of the structural unit (A) and the structural unit (C) is determined. AA is the structural unit (A) -structural unit (A) dyad, AC is the structural unit (A) -structural unit (C) dyad, and CC is the structural unit (C) -constituent unit (C) dyad. is there.
Number of structural units (A) = 100−Number of structural units (C) Number of structural units (C) = 100 × (AC / 2 + CC) / (AA + AC + CC)
Since the structural unit (B) in the polymer (1) is formed by the reaction of the structural unit (C) contained in the precursor polymer (1) and the compound (α), the reaction The conversion rate of the structural unit (C) is determined by the following method.
The integral value (hereinafter, integral value Y) of the signal belonging to the specific carbon contained in the side chain of the structural unit (C) of the precursor polymer (1), and the structural unit (B) of the polymer (1) The conversion value is obtained by substituting the integral value of the signal attributed to the specific carbon contained in the side chain (hereinafter, integral value Z) into the following equation.
Conversion rate = Z / (Y + Z)
In the reaction between the precursor polymer (1) and the compound (α), the structural unit (A) contained in the precursor polymer (1) does not change, so that the structural unit (A) contained in the polymer (1) does not change. The number and the number of the structural units (A) contained in the precursor polymer (1) are the same. The number of structural units (B) contained in the polymer (1) is determined as the product of the number of structural units (C) contained in the precursor polymer (1) and the conversion rate. The number of structural units (C) contained in the polymer (1) is the number of structural units (C) contained in the precursor polymer (1) and the number of structural units (B) contained in the polymer (1). It is calculated as a difference.

  Examples of the method for producing the polymer (1) include a precursor polymer (1), at least one compound (α), that is, an alcohol having an alkyl group having 14 to 30 carbon atoms, and the number of carbon atoms. An amine having an alkyl group having 14 to 30 carbon atoms, an alkyl halide having an alkyl group having 14 to 30 carbon atoms, a carboxylic acid having an alkyl group having 14 to 30 carbon atoms, an alkyl having 14 to 30 carbon atoms A carboxylic acid amide having a group, a carboxylic acid halide having an alkyl group having 14 to 30 carbon atoms, a carbamic acid having an alkyl group having 14 to 30 carbon atoms, and an alkyl group having 14 to 30 carbon atoms From the group consisting of an alkyl urea and an isocyanate having an alkyl group having 14 to 30 carbon atoms And a method of polymerizing a monomer as a raw material of the structural unit (B) and a method of copolymerizing ethylene and a monomer as a raw material of the structural unit (B). . The alkyl group of the compound (α) may be, for example, a linear alkyl group or a branched alkyl group, but is preferably a linear alkyl group.

  The said precursor polymer (1) is a raw material for manufacturing the said polymer (1), and a precursor polymer (1) does not contain the structural unit (B) shown by Formula (1). The precursor polymer (1) may include a structural unit that does not correspond to any of the structural unit (A), the structural unit (B), and the structural unit (C).

  In the precursor polymer (1), preferably, when the total number of the structural units (A) and the structural units (C) is 100%, the number of the structural units (A) is 0% or more and 99%. The total number of the structural units (C) is 1% or more and 100% or less. More preferably, the number of the structural units (A) is 70% or more and 99% or less, and the total number of the structural units (C) is 1% or more and 30% or less.

  Examples of the method for forming the structural unit (B) in the polymer (1) include a method of reacting the structural unit (C) contained in the precursor polymer (1) with the compound (α), and Examples thereof include a method of polymerizing a monomer that is a raw material of the structural unit (B) and a method of copolymerizing a monomer that is a raw material of the structural unit (B) with ethylene. The alkyl group of the compound (α) is preferably a linear alkyl group. In the polymerization of monomers, a polymerization initiator such as an azo compound may be used. Examples of the azo compound include azobisisobutyronitrile.

  Examples of the precursor polymer (1) include acrylic acid polymer, methacrylic acid polymer, vinyl alcohol polymer, methyl acrylate polymer, ethyl acrylate polymer, n-propyl acrylate polymer, n-butyl acrylate polymer, and methyl. Methacrylate polymer, ethyl methacrylate polymer, n-propyl methacrylate polymer, n-butyl methacrylate polymer, vinyl formate polymer, vinyl acetate polymer, vinyl propionate polymer, vinyl (n-butyrate) polymer, Methyl vinyl ether polymer, ethyl vinyl ether polymer, n-propyl vinyl ether polymer, n-butyl vinyl ether polymer, maleic anhydride polymer, glycidyl acrylate polymer, glycidyl methacrylate polymer, 3- (dimethylamino) Propyl acrylate polymer, 3- (dimethylamino) propyl methacrylate polymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-vinyl alcohol copolymer, ethylene-methyl acrylate copolymer, ethylene- Ethyl acrylate copolymer, ethylene-n-propyl acrylate copolymer, ethylene-n-butyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-n-propyl methacrylate copolymer Polymer, ethylene-n-butyl methacrylate copolymer, ethylene-vinyl formate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, ethylene-vinyl (n-butyrate) copolymer Ethylene-methyl vinyl ether copolymer, ethylene-ethyl vinyl ether copolymer, ethylene-n-propyl vinyl ether copolymer, ethylene-n-butyl vinyl ether copolymer, ethylene-maleic anhydride copolymer, ethylene-glycidyl acrylate copolymer Examples include polymers, ethylene-glycidyl methacrylate copolymers, ethylene-3- (dimethylamino) propyl acrylate copolymers, and ethylene-3- (dimethylamino) propyl methacrylate copolymers.

  Examples of the alcohol having a linear alkyl group having 14 to 30 carbon atoms include n-tetradecyl alcohol, n-pentadecyl alcohol, n-hexadecyl alcohol, n-heptadecyl alcohol, n-octadecyl alcohol, n- Nonadecyl alcohol, n-eicosyl alcohol, n-henecosyl alcohol, n-docosyl alcohol, n-tricosyl alcohol, n-tetracosyl alcohol, n-pentacosyl alcohol, n-hexacosyl alcohol, Examples include n-heptacosyl alcohol, n-octacosyl alcohol, n-nonacosyl alcohol, and n-triacontyl alcohol.

  Examples of the alcohol having a branched alkyl group having 14 to 30 carbon atoms include isotetradecyl alcohol, isopentadecyl alcohol, isohexadecyl alcohol, isoheptadecyl alcohol, isooctadecyl alcohol, isononadecyl alcohol, and isoeicosyl. Alcohol, isohenecosyl alcohol, isodocosyl alcohol, isotricosyl alcohol, isotetracosyl alcohol, isopentacosyl alcohol, isohexacosyl alcohol, isoheptacosyl alcohol, isooctacosyl alcohol, isononacosyl Alcohol and isotriacontyl alcohol are mentioned.

  Examples of the amine having a linear alkyl group having 14 to 30 carbon atoms include n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n- Nonadecylamine, n-eicosylamine, n-henecosylamine, n-docosylamine, n-tricosylamine, n-tetracosylamine, n-pentacosylamine, n-hexacosylamine, n-heptacosylamine, n- Examples include octacosylamine, n-nonacosylamine, and n-triacontylamine.

  Examples of the amine having a branched alkyl group having 14 to 30 carbon atoms include, for example, isotetradecylamine, isopentadecylamine, isohexadecylamine, isoheptadecylamine, isooctadecylamine, isononadecylamine, and isoeicosyl. Amine, isohenecosylamine, isodocosylamine, isotricosylamine, isotetracosylamine, isopentacosylamine, isohexacosylamine, isoheptacosylamine, isooctacosylamine, isononacosylamine, and isotriacontylamine Is mentioned.

  Examples of the alkyl halide having a linear alkyl group having 14 to 30 carbon atoms include n-tetradecyl iodide, n-pentadecyl iodide, n-hexadecyl iodide, n-heptadecyl iodide, n- Octadecyl iodide, n-nonadecyl iodide, n-eicosyl iodide, n-heneicosyl iodide, n-docosyl iodide, n-tricosyl iodide, n-tetracosyl iodide, n-pentacosyl iodide Examples include iodide, n-hexacosyl iodide, n-heptacosyl iodide, n-octacosyl iodide, n-nonacosyl iodide, and n-triacontyl iodide.

  Examples of the alkyl halide having a branched alkyl group having 14 to 30 carbon atoms include isotetradecyl iodide, isopentadecyl iodide, isohexadecyl iodide, isoheptadecyl iodide, isooctadecyl iodide, and isonona. Decyl iodide, isoeicosyl iodide, isohenecosyl iodide, isodocosyl iodide, isotricosyl iodide, isotetracosyl iodide, isopentacosyl iodide, isohexacosyl iodide, iso Examples include heptacosyl iodide, isooctacosyl iodide, isononacosyl iodide, and isotriacontyl iodide.

  Examples of the carboxylic acid having a linear alkyl group having 14 to 30 carbon atoms include n-tetradecanoic acid, n-pentadecanoic acid, n-hexadecanoic acid, n-heptadecanoic acid, n-octadecanoic acid, n-nonadecanoic acid, n-eicosanoic acid, n-heneicosanoic acid, n-docosanoic acid, n-tricosanoic acid, n-tetracosanoic acid, n-pentacosanoic acid, n-hexacosanoic acid, n-heptacosanoic acid, n-octacosanoic acid, n-nonacosanoic acid, And n-triacontanoic acid.

  Examples of the carboxylic acid having a branched alkyl group having 14 to 30 carbon atoms include, for example, isotetradecanoic acid, isopentadecanoic acid, isohexadecanoic acid, isoheptadecanoic acid, isooctadecanoic acid, isonononadecanoic acid, isoeicosanoic acid, isoheneicosanoic acid, Examples include isodocosanoic acid, isotricosanoic acid, isotetracosanoic acid, isopentacosanoic acid, isohexacosanoic acid, isoheptacosanoic acid, isooctacosanoic acid, isononacosanoic acid, and isotriacontanoic acid.

  Examples of the carboxylic acid amide having a linear alkyl group having 14 to 30 carbon atoms include n-tetradecanoic acid amide, n-pentadecanoic acid amide, n-hexadecanoic acid amide, n-heptadecanoic acid amide, and n-octadecanoic acid amide. N-nonadecanoic acid amide, n-eicosanoic acid amide, n-heneicosanoic acid amide, n-docosanoic acid amide, n-tricosanoic acid amide, n-tetracosanoic acid amide, n-pentacosanoic acid amide, n-hexacosanoic acid amide, n -Heptacosanoic acid amide, n-octacosanoic acid amide, n-nonacosanoic acid amide, and n-triacontanoic acid amide.

  Examples of the carboxylic acid amide having a branched alkyl group having 14 to 30 carbon atoms include, for example, isotetradecanoic acid amide, isopentadecanoic acid amide, isohexadecanoic acid amide, isooctadecanoic acid amide, isooctadecanoic acid amide, isonononadecanoic acid amide, and isoeicosanoic acid. Amides, isoheneicosanoic acid amides, isodocosanoic acid amides, isotricosanoic acid amides, isotetracosanoic acid amides, isopentacosanoic acid amides, isohexacosanoic acid amides, isoheptacosanoic acid amides, isooctacosanoic acid amides, isononacosanoic acid amides, and isotriacantanoic acid amides. .

  Examples of the carboxylic acid halide having a linear alkyl group having 14 to 30 carbon atoms include n-tetradecanoic acid chloride, n-pentadecanoic acid chloride, n-hexadecanoic acid chloride, n-heptadecanoic acid chloride, and n-octadecanoic acid chloride. N-nonadecanoic acid chloride, n-eicosanoic acid chloride, n-heneicosanoic acid chloride, n-docosanoic acid chloride, n-tricosanoic acid chloride, n-tetracosanoic acid chloride, n-pentacosanoic acid chloride, n-hexacosanoic acid chloride, n -Heptacosanoic acid chloride, n-octacosanoic acid chloride, n-nonacosanoic acid chloride, and n-triacontanoic acid chloride.

  Examples of the carboxylic acid halide having a branched alkyl group having 14 to 30 carbon atoms include isotetradecanoic acid chloride, isopentadecanoic acid chloride, isohexadecanoic acid chloride, isoheptadecanoic acid chloride, isooctadecanoic acid chloride, isonononadecanoic acid chloride, and isoeicosanoic acid. Chloride, Isoheneicosanoic Acid Chloride, Isodocosanoic Acid Chloride, Isotricosanoic Acid Chloride, Isotetracosanoic Acid Chloride, Isopentacosanoic Acid Chloride, Isohexacosanoic Acid Chloride, Isoheptacosanoic Acid Chloride, Isooctacosanoic Acid Chloride, Isononaconic Acid Chloride, and Isotria Contanic Acid Chloride. .

  Examples of the carbamic acid having a linear alkyl group having 14 to 30 carbon atoms include n-tetradecylcarbamic acid, n-pentadecylcarbamic acid, n-hexadecylcarbamic acid, n-heptadecylcarbamic acid, n- Octadecylcarbamic acid, n-nonadecylcarbamic acid, n-eicosylcarbamic acid, n-heneicosylcarbamic acid, n-docosylcarbamic acid, n-tricosylcarbamic acid, n-tetracosylcarbamic acid, n- Examples include pentacosylcarbamic acid, n-hexacosylcarbamic acid, n-heptacosylcarbamic acid, n-octacosylcarbamic acid, n-nonacosylcarbamic acid, and n-triacontylcarbamic acid.

  Examples of the carbamic acid having a branched alkyl group having 14 to 30 carbon atoms include isotetradecyl carbamic acid, isopentadecyl carbamic acid, isohexadecyl carbamic acid, isoheptadecyl carbamic acid, isooctadecyl carbamic acid, and isonona. Decylcarbamic acid, isoeicosylcarbamic acid, isoheneicosylcarbamic acid, isodocosylcarbamic acid, isotricosylcarbamic acid, isotetracosylcarbamic acid, isopentacosylcarbamic acid, isohexacosylcarbamic acid, iso Examples include heptacosylcarbamic acid, isooctacosylcarbamic acid, isononacosylcarbamic acid, and isotriacontylcarbamic acid.

  Examples of the alkyl urea having a linear alkyl group having 14 to 30 carbon atoms include n-tetradecyl urea, n-pentadecyl urea, n-hexadecyl urea, n-heptadecyl urea, n-octadecyl urea, n-nonadecyl urea, n-eicosyl urea, n-henecosyl urea, n-docosyl urea, n-tricosyl urea, n-tetracosyl urea, n-pentacosyl urea, n-hexacosyl urea, n-heptacosyl urea, n-octacosyl urea, n-nonacosyl urea, And n-triacontyl urea.

  Examples of the alkylurea having a branched alkyl group having 14 to 30 carbon atoms include isotetradecylurea, isopentadecylurea, isohexadecylurea, isoheptadecylurea, isooctadecylurea, isononadecylurea, isoeicosylurea, isoheneico. Examples include silurea, isodocosyl urea, isotricosyl urea, isotetracosyl urea, isopentacosyl urea, isohexacosyl urea, isoheptacosyl urea, isooctacosyl urea, isononacosyl urea, and isotriacontyl urea.

  Examples of the isocyanate having a linear alkyl group having 14 to 30 carbon atoms include n-tetradecyl isocyanate, n-pentadecyl isocyanate, n-hexadecyl isocyanate, n-heptadecyl isocyanate, n-octadecyl isocyanate, n- Nonadecyl isocyanate, n-eicosyl isocyanate, n-henecosyl isocyanate, n-docosyl isocyanate, n-tricosyl isocyanate, n-tetracosyl isocyanate, n-pentacosyl isocyanate, n-hexacosyl isocyanate, Examples include n-heptacosyl isocyanate, n-octacosyl isocyanate, n-nonacosyl isocyanate, and n-triacontyl isocyanate.

  Examples of the isocyanate having a branched alkyl group having 14 to 30 carbon atoms include, for example, isotetradecyl isocyanate, isopentadecyl isocyanate, isohexadecyl isocyanate, isoheptadecyl isocyanate, isooctadecyl isocyanate, isonononadecyl isocyanate, isoeicosyl. Isocyanate, isoheneicosyl isocyanate, isodocosyl isocyanate, isotricosyl isocyanate, isotetracosyl isocyanate, isopentacosyl isocyanate, isohexacosyl isocyanate, isoheptacosyl isocyanate, isooctacosyl isocyanate, isononacosyl Isocyanates, and isotriacontyl isocyanate.

When the precursor polymer (1) contains a structural unit (A) derived from ethylene, the reactivity ratio of ethylene used as a raw material during the production of the precursor polymer (1) is r1, and the structural unit (C) is The product r1r2 of the reactivity ratio when the reactivity ratio of the monomer to be formed is r2 is preferably so that the shape retention of the resin composition (eg, heat storage material) containing the precursor polymer (1) is good. Is 0.5 or more and 5.0 or less, more preferably 0.5 or more and 3.0 or less.
The reactivity ratio r1 of ethylene is k11, the reaction rate at which the ethylene is bonded to the polymer whose terminal is the structural unit (A) at the time of copolymerization of ethylene and the monomer forming the structural unit (C), and the terminal is composed of This is a value defined by the formula r1 = k11 / k12, where k12 is the reaction rate at which the monomer that forms the structural unit (C) binds to the polymer that is the unit (A). The reactivity ratio r1 is determined by the copolymerization of ethylene and the monomer that forms the structural unit (C), in which case the polymer whose terminal is the structural unit (A) is ethylene or the monomer that forms the structural unit (C). It is an index showing whether it is more likely to react with. The larger r1 is, the more easily the polymer whose terminal is the structural unit (A) reacts with ethylene, and the chain of the structural unit (A) is easily generated.
The reactivity ratio r2 of the monomer that forms the structural unit (C) is such that ethylene is bonded to the polymer whose terminal is the structural unit (C) when copolymerizing ethylene with the monomer that forms the structural unit (C). R2 = k22 / k21, where k21 is the reaction rate and k22 is the reaction rate at which the monomer that forms the structural unit (C) binds to the polymer whose terminal is the structural unit (C). . The reactivity ratio r2 is determined by the copolymerization of ethylene and the monomer that forms the structural unit (C), in which case the polymer whose terminal is the structural unit (C) is ethylene or the monomer that forms the structural unit (C). It is an index showing whether it is more likely to react with. The larger r2 is, the more easily the polymer whose terminal is the structural unit (C) reacts with the monomer forming the structural unit (C), and the chain of the structural unit (C) is likely to be generated.
The product of reactivity ratio r1r2 is calculated by the method described in the literature “Kakugo, M .; Naito, Y .; Mizunuma, K .; Miyatake, T. Macromolecules, 1982, 15, 1150”. In the present invention, the product r1r2 is obtained by calculating the structural unit (A) calculated from the ¹³ C nuclear magnetic resonance spectrum of the precursor polymer (1) and the diads AA, AC, and CC of the structural unit (C). It is obtained by substituting a number into the equation shown below.
r1r2 = AA [CC / (AC / 2) ² ]
The reactivity ratio product r1r2 is an index representing the monomer chain distribution of the copolymer. The closer the r1r2 is to 1, the higher the randomness of the monomer chain distribution of the copolymer. The closer the r1r2 is to 0, the higher the monomer chain distribution of the copolymer is, and the higher the r1r2 is, The larger the monomer chain distribution of the copolymer, the higher the block copolymer property.

  The melt flow rate of the precursor polymer (1) measured at a temperature of 190 ° C. and a load of 21 N in accordance with JIS K7210 is preferably 0.1 g / 10 min or more and 500 g / 10 min or less.

  Examples of the method for producing the precursor polymer (1) include a coordination polymerization method, a cationic polymerization method, an anionic polymerization method, and a radical polymerization method, preferably a radical polymerization method, more preferably a radical under high pressure. It is a polymerization method.

  The reaction temperature for reacting the precursor polymer (1) with at least one kind of the compound (α) is usually 40 ° C. or higher and 250 ° C. or lower. This reaction may be performed in the presence of a solvent, and examples of the solvent include hexane, heptane, octane, nonane, decane, toluene, and xylene. In addition, when a by-product is generated in this reaction, the reaction may be carried out while distilling off the by-product under reduced pressure in order to promote the reaction. The product and the solvent are cooled, the distillate containing the by-product and the solvent is separated into a by-product layer and a solvent layer, and the reaction is performed while only the recovered solvent is returned to the reaction system as a reflux liquid. May be performed.

  Moreover, you may perform reaction of the said precursor polymer (1) and at least 1 type of said compound ((alpha)), melt-kneading the said precursor polymer (1) and the said compound ((alpha)). Further, when a by-product is produced when the precursor polymer (1) and the compound (α) are reacted while being melt-kneaded, the by-product is distilled off under reduced pressure to promote the reaction. The reaction may be carried out. Examples of the melt kneading apparatus used for the melt kneading include apparatuses such as a single screw extruder, a twin screw extruder, and a Banbury mixer. The temperature of the melt-kneading apparatus is preferably 100 ° C. or higher and 250 ° C. or lower.

  When the precursor polymer (1) is reacted with at least one kind of the compound (α), a catalyst may be added to promote the reaction. Examples of the catalyst include alkali metal salts and group 4 metal complexes. Examples of the alkali metal salt include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, and alkali metal alkoxides such as lithium methoxide and sodium methoxide. Examples of the group 4 metal complex include tetra (isopropyl) orthotitanate, tetra (n-butyl) orthotitanate, and tetraoctadecyl orthotitanate. The addition amount of the catalyst is 0.01 part by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the total amount of the precursor polymer (1) used in the reaction and at least one kind of the compound (α). It is preferable that it is 0.01 parts by weight or more and 5 parts by weight or less.

  The polymer (1) has a shape-retaining property of a molded body containing the resin composition according to the present invention at a melting peak temperature or higher of the polymer (1), and a molding of the resin composition containing the polymer (1). It preferably has a structural unit (A) derived from ethylene so that processability is good. More preferably, the structural unit (A) derived from ethylene forms a branched structure in the polymer so that the blow moldability and foam moldability of the resin composition containing the polymer (1) are good. More preferably, the branched structure is a long chain branched structure that is long enough to allow entanglement of polymer chains by the branched structure.

The ratio A defined by the following formula (I) of the polymer (1) is preferably 0.95 or less, more preferably 0.90 or less, and still more preferably 0.80 or less.
A = α ₁ / α ₀ (I)
[In the formula (I), α ₁ is
Measure the absolute molecular weight and intrinsic viscosity of the polymer by gel permeation chromatography using a device with a light scattering detector and a viscosity detector,
The measured data is plotted with the logarithm of the absolute molecular weight as the horizontal axis and the logarithm of the intrinsic viscosity as the vertical axis. This is a value obtained by a method including approximation by the least squares method with the formula (II) in a range equal to or lower than the logarithm of the molecular weight and setting the value of the slope of the straight line representing the formula (II) as α ₁ .
log [η ₁ ] = α ₁ logM ₁ + logK ₁ (I−I)
(In formula (II), [η ₁ ] represents the intrinsic viscosity (unit: dl / g) of the polymer, M ₁ represents the absolute molecular weight of the polymer, and K ₁ is a constant.)
In the formula (I), α ₀ is
The absolute molecular weight and intrinsic viscosity of polyethylene standard substance 1475a (manufactured by National Institute of Standards and Technology) are measured by gel permeation chromatography using a device equipped with a light scattering detector and a viscosity detector.
The measured data is plotted with the logarithm of absolute molecular weight as the horizontal axis and the logarithm of intrinsic viscosity as the vertical axis. in logarithmic the range of z-average molecular weight approximating the minimum square method by the formula (I-II), a value obtained by a process comprising the value of the slope of the straight line representing the formula (I-II) and alpha ₀ is there.
log [η ₀ ] = α ₀ logM ₀ + log K ₀ (I-II)
(In the formula (I-II), [η ₀ ] represents the intrinsic viscosity (unit: dl / g) of the polyethylene standard material 1475a, M ₀ represents the absolute molecular weight of the polyethylene standard material 1475a, and K ₀ is a constant. In the measurement of the absolute molecular weight and intrinsic viscosity of the polymer and polyethylene standard substance 1475a by gel permeation chromatography, the mobile phase is orthodichlorobenzene and the measurement temperature is 155 ° C.)]
The absolute molecular weight is determined from the data obtained by the light scattering detector, and the intrinsic viscosity ([η]) is determined by the viscosity detector. Calculation is performed with reference to “Exclusion Chromatography, Springer (1999)”.
The polyethylene reference material 1475a (manufactured by National Institute of Standards and Technology) is a high-density polyethylene that does not contain branches. Formula (II) and formula (I-II) is referred to as the expression of Mark-Hauwink-Sakurada representing the correlation of the intrinsic viscosity and molecular weight of the polymer, as the alpha ₁ is small, the polymer according to the branch structure There are many chain entanglements. Since the polyethylene standard material 1475a does not form a branched structure, the polymer chain is not entangled by the branched structure. The smaller the A, which is the ratio of α _{1 to} α ₀ of the polyethylene standard material 1475a, the greater the amount of the long chain branched structure formed by the structural unit (A) in the polymer.

The weight average molecular weight of the polymer (1) measured by gel permeation chromatography using an apparatus equipped with a light scattering detector is preferably 10,000 to 1,000,000, more preferably. Is from 50,000 to 750,000, more preferably from 100,000 to 500,000.
In the measurement of the weight average molecular weight of the polymer (1) by gel permeation chromatography, the mobile phase is orthodichlorobenzene and the measurement temperature is 155 ° C.

The flow activation energy (E _a ) of the polymer (1) is preferably 40 kJ / mol or more, more preferably 50 kJ / mol or more, from the viewpoint of further reducing the extrusion load during molding. More preferably, it is 60 kJ / mol or more. In addition, E _a is preferably 100 kJ / mol or less, more preferably 90 kJ / mol or less, and further preferably 80 kJ / mol or less so that the appearance of a molded product obtained by extrusion molding is good. . The size of the E _a is mainly dependent on the long chain branch number in the polymer. A polymer containing more long chain branches has _a higher Ea.

The activation energy (E _a ) of the flow of the polymer is determined by the method shown below. First, the melt complex viscosity of the polymer at each temperature (T, unit: ° C.) of three or more temperatures including 170 ° C. among the temperatures of 90 ° C., 110 ° C., 130 ° C., 150 ° C., and 170 ° C. -Measure the angular frequency curve. The melt complex viscosity-angular frequency curve is a double logarithmic curve with the logarithm of melt complex viscosity (unit: Pa · sec) as the vertical axis and the logarithm of angular frequency (unit: rad / sec) as the horizontal axis. Next, for the melt complex viscosity-angular frequency curve measured at each temperature other than 170 ° C., the angular frequency is a _T times, and the melt complex viscosity is overlapped with the melt complex viscosity-angular frequency curve at 170 ° C. _Is multiplied by 1 / a _T. a _T is a value determined as appropriate so that the melt complex viscosity-angular frequency curve measured at each temperature other than 170 ° C. overlaps the melt complex viscosity-angular frequency curve at 170 ° C.
The a _T is generally referred to as a shift factor, and has a value that varies depending on the measurement temperature of the melt complex viscosity-angular frequency curve.
Next, at each temperature (T), [ln (a _T )] and [1 / (T + 273.16)] are obtained, and [ln (a _T )] and [1 / (T + 273.16)] are obtained. Is approximated by the least square method using the following equation (II) to determine the slope m of the straight line representing the equation (II). Substituting said m in formula (III), obtains the _{E a.}
ln (a _T ) = m (1 / (T + 273.16)) + n (II)
E _a = | 0.008314 × m | (III)
a _T : Shift factor E _a : Flow activation energy (unit: kJ / mol)
T: Temperature (unit: ° C)
Commercially available calculation software may be used for the calculation, and examples of the calculation software include Ochestrator manufactured by TA Instruments.
The above method is based on the following principle.
It is known that the melt complex viscosity-angular frequency curve (logarithmic curve) measured at different temperatures overlaps with one parent curve (referred to as a master curve) by horizontally moving each temperature curve by a predetermined amount. This is referred to as the “temperature-time superposition principle”. The horizontal movement amount is called a shift factor, and the shift factor is a value depending on temperature. It is known that the temperature dependency of the shift factor is expressed by the above formulas (II) and (III). Equations (II) and (III) are called Arrhenius equations.

The correlation coefficient when [ln (a _T )] and [1 / (T + 273.16)] are approximated by the least square method using the above equation (II) is set to 0.9 or more.

  The melt complex viscosity-angular frequency curve is measured by using a viscoelasticity measuring apparatus (for example, ARES manufactured by TA Instruments, Inc.). Usually, geometry: parallel plate, plate diameter: 25 mm, plate interval: 1. It is performed under the conditions of 2 to 2 mm, strain: 5%, angular frequency: 0.1 to 100 rad / sec. The measurement is performed under a nitrogen atmosphere. Moreover, it is preferable to mix | blend an appropriate quantity (for example, 1000 weight ppm) of antioxidant previously with a measurement sample.

  The elongational viscosity nonlinear index k representing the strength of strain hardening of the polymer (1) is, for example, small neck-in at the time of T-die film processing, small thickness unevenness of the resulting film, and difficult to break during foam molding, From the viewpoint of such excellent moldability, it is preferably 0.85 or more, more preferably 0.90 or more, and still more preferably 0.95 or more. The strain hardening of the polymer means that when the polymer is strained, the extensional viscosity increases rapidly above a certain amount of strain. In addition, the index k is 2.00 or less from the viewpoint of ease of molding the polymer (1) and the resin composition of the present invention containing the polymer (1) into a desired shape. Preferably, it is 1.50 or less, more preferably 1.40 or less, still more preferably 1.30 or less, and particularly preferably 1.20 or less.

The elongational viscosity nonlinear index k is determined by the following method.
110 ° C. temperature and one second viscosity eta _{E 1} in elongation time t when the at a strain rate of the polymer was uniaxially stretched ^-1 (t), the weight at a strain rate of temperature and 0.1 sec ^-1 of 110 ° C. The viscosity η _E 0.1 (t) at the extension time t when the combined uniaxial extension is obtained. The η _E 1 (t) and the η _E 0.1 (t) at any same extension time t are substituted into the following equation to obtain α (t).
α (t) = η _E 1 (t) / η _E 0.1 (t)
The logarithm of α (t) (ln (α (t))) is plotted against the extension time t. When t is in the range of 2.0 seconds to 2.5 seconds, ln (α (t)) and t are Approximate the least squares method with the following formula. The value of the slope of the straight line representing the following formula is k.
ln (α (t)) = kt
The k is used when the correlation function r2 used for the least square method approximation in the above equation is 0.9 or more.
The measurement of the viscosity when the uniaxial stretching is performed is performed in a nitrogen atmosphere using a viscoelasticity measuring apparatus (for example, ARES manufactured by TA Instruments).

In the measurement of elongational viscosity, a polymer having a long chain branch has a property that the elongational viscosity rapidly deviates from the linear region in a high strain region, that is, so-called strain hardening. In the case of a polymer having strain hardening properties, it is known that the logarithm of α (t) (ln (α (t))) increases in proportion to ln (l / l ₀ ) (here Where l ₀ and l are the lengths of the sample at elongation times 0 and t, respectively (reference: Kiyama Kiyoto, Osamu Ishizuka; Textile Society, 37, T-258 (1981)). In the case of a polymer without strain hardening, α (t) is 1 for an arbitrary extension time, and the logarithm of α (t) (ln (α (t))) is plotted against the extension time. The slope k of the straight line is zero. In the case of a polymer having strain hardening properties, the slope k of the straight line plot is not 0, particularly in a high strain region. In the present invention, the slope of a straight line obtained by plotting the logarithm (ln (α (t))) of the nonlinear parameter α (t) against the extension time is defined as k as a parameter representing the degree of strain hardening.

  The polymer (1) may form a mixture with an unreacted compound (α) or a catalyst added to accelerate the reaction. The content of the unreacted compound (α) contained in the mixture is less than 3 parts by weight with respect to 100 parts by weight of the polymer in order to suppress the adhesion of the polymer to a substrate such as glass or metal. preferable.

The polymer (1) may be a cross-linked polymer or a non-cross-linked polymer.
In one embodiment, the polymer (1) is an uncrosslinked polymer (hereinafter referred to as polymer (α)).
The polymer (α) has a polymer gel fraction described below of less than 20%.
The polymer (α) is the total number of the structural unit (A), the structural unit (B), and the structural unit (C) when the total number of all the structural units contained in the polymer is 100%. Is preferably 90% or more, more preferably 95% or more, and even more preferably 100%.

<Crosslinked polymer>
In one embodiment, the polymer (1) is crosslinked. That is, at least a part of the molecules of the polymer (1) are linked by covalent bonds between the molecules. Note that “the polymer (1) is crosslinked” means that the polymers (1) are linked to each other by a covalent bond between the molecules, and that the polymer (1) and the polymer (1 ) And a different polymer (to be described later) are linked to each other by a covalent bond between molecules.
Examples of the method of crosslinking the polymer include a method of crosslinking by irradiating with ionizing radiation and a method of crosslinking using an organic peroxide.

  When the polymer is irradiated with ionizing radiation and crosslinking is performed, the polymer (α) that has been previously shaped into a desired shape is usually irradiated with ionizing radiation. A known method can be used for molding, and extrusion molding, injection molding, and press molding are preferable. The molded product irradiated with ionizing radiation may be a molded product of a resin composition containing the polymer (1) and a polymer different from the polymer (1). Examples of the polymer different from the polymer (1) include polystyrene (2) and a copolymer (3) described later. When the molded product contains the polymer (1), polystyrene (2) and copolymer (3), the total amount of the polymer (1), polystyrene (2) and copolymer (3) is When the content is 100% by weight, the content of the polymer (1) is preferably 10% by weight or more and 90% by weight or less.

  Examples of the ionizing radiation include α rays, β rays, γ rays, electron rays, neutron rays, and X rays, and cobalt-60 γ rays or electron rays are preferable. When the molded body containing the polymer is in the form of a sheet, the ionizing radiation may be irradiated from at least one surface of the sheet-shaped molded body.

  The irradiation with ionizing radiation is performed using an ionizing radiation irradiation apparatus, and the irradiation amount is usually 5 to 300 kGy, preferably 10 to 150 kGy. The polymer (1) can obtain a polymer having a high degree of crosslinking with a lower irradiation amount than usual.

  In the case of obtaining a crosslinked polymer by irradiation with ionizing radiation, it is possible to obtain a crosslinked polymer having a higher degree of crosslinking by including a crosslinking aid in the molded product irradiated with ionizing radiation. it can. The crosslinking aid is for increasing the degree of crosslinking of the polymer and improving mechanical properties, and a compound having a plurality of double bonds in the molecule is preferably used. Examples of the crosslinking aid include N, N′-m-phenylene bismaleimide, toluylene bismaleimide, triallyl isocyanurate, triallyl cyanurate, p-quinone dioxime, nitrobenzene, diphenylguanidine, divinylbenzene, ethylene glycol. Mention may be made of dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, and allyl methacrylate. Moreover, you may use these crosslinking adjuvants in combination of multiple.

  When the total weight of the polymer (1) contained in the molded product irradiated with ionizing radiation and the polymer different from the polymer (1) is 100 parts by weight, It is preferable that it is 0.01-4.0 weight part, and it is more preferable that it is 0.05-2.0 weight part.

As a method of crosslinking using an organic peroxide, for example, there is a method of crosslinking the polymer (α) by a molding method involving heating the resin composition containing the polymer (α) and the organic peroxide. Can be mentioned. Examples of the molding method involving heating include extrusion molding, injection molding, and press molding. The resin composition containing the polymer (α) and the organic peroxide may contain the polymer (1) and a polymer different from the polymer.
When the resin composition containing the polymer (α) and the organic peroxide contains a polymer different from the polymer (1), examples of the polymer include polystyrene (2) and a copolymer described later. (3), and when the total amount of the polymer (1), polystyrene (2) and copolymer (3) is 100% by weight, the content of the polymer (1) is 10% by weight. The content is preferably 90% by weight or less.

  In the case of crosslinking with an organic peroxide, an organic peroxide having a decomposition temperature equal to or higher than the flow start temperature of the resin component contained in the composition containing the polymer (α) and the organic peroxide is preferably used. Preferred organic peroxides include, for example, dicumyl peroxide, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 2,5-dimethyl-2,5-di-tert-butylperoxide. Examples include oxyhexine, α, α-di-tert-butylperoxyisopropylbenzene, tert-butylperoxy-2-ethylhexyl carbonate, and the like.

  The crosslinked polymer (1) may contain an additive as necessary. Examples of such additives include flame retardants, antioxidants, weathering agents, lubricants, antiblocking agents, antistatic agents, antifogging agents, drip-free agents, pigments, and fillers. These additives can be added by kneading with a polymer before crosslinking.

  The crosslinked polymer (1) preferably has a gel fraction of 20% by weight or more, more preferably 40% by weight or more, still more preferably 60% by weight or more, and most preferably 70% by weight. % Or more. The gel fraction indicates the degree of cross-linking of the polymer that has been cross-linked, and the higher the gel fraction of the polymer means that the polymer has more cross-linked structures and a stronger network. It means that a structure is formed. If the gel fraction of the polymer is higher, the polymer has higher shape retention and is more difficult to deform.

In addition, a gel fraction is calculated | required by the method described below. Weigh about 500 mg of polymer and an empty net cage made of a wire mesh (aperture: 400 mesh). Net cage and xylene encapsulating a polymer (Kanto Chemical Co., Ltd. deer special grade or equivalent thereof: o-, m-, p-xylene and ethylbenzene mixture, total weight of o-, m-, p-xylene is 85 (50% by weight or more) 50 mL is introduced into a 100 mL test tube and subjected to heat extraction at 110 ° C. for 6 hours. After extraction, the net residue containing the extraction residue is taken out from the test tube, dried under reduced pressure at 80 ° C. for 8 hours in a vacuum dryer, and the net residue containing the extraction residue after drying is weighed. The gel weight is calculated from the difference in weight between the net with extraction residue after drying and the empty net with an extraction residue. The gel fraction (% by weight) is calculated based on the following formula.
Gel fraction = (gel weight / measured sample weight) × 100

<Polystyrene (2)>
As polystyrene (2), in order to improve the moldability of the resin composition, the mass average molecular weight Mw measured by gel permeation chromatography is preferably 100,000 ≦ Mw ≦ 350,000.

<Copolymer (3)>
As a copolymer having a monomer unit derived from an aromatic vinyl compound and a monomer unit derived from a conjugated diene compound (hereinafter referred to as copolymer (3)), aromatic vinyl compound-conjugated Examples include diene compound copolymers, aromatic vinyl compounds-conjugated diene compounds-aromatic vinyl compound copolymers, and hydrogenated products thereof.

  Examples of the aromatic vinyl compound in the copolymer (3) include styrene, α-methylstyrene, o-, m-, p-methylstyrene, 1,3-dimethylstyrene, vinylxylene, monochlorostyrene, and dichlorostyrene. , Monobromostyrene, dibromostyrene, ethylstyrene, vinylnaphthalene and the like, and styrene is preferable.

  Examples of the conjugated diene compound in the copolymer (3) include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-neopentyl-1,3-butadiene, and 2-chloro-1,3-butadiene. 2-cyano-1,3-butadiene and the like, and butadiene or isoprene is preferable.

  Specific examples of the copolymer (3) include a hydrogenated product of a styrene-butadiene-styrene block copolymer and a hydrogenated product of a styrene-isoprene-styrene block copolymer.

The content of the monomer unit derived from the aromatic vinyl compound is preferably 10% by weight or more and 50% by weight or less, more preferably 10% by weight or more and 40% by weight or less in order to improve the moldability of the resin composition. % By weight or less. However, the total amount of the copolymer having monomer units derived from an aromatic vinyl compound and monomer units derived from a conjugated diene compound is 100% by weight.
In addition, content of the monomer unit derived from an aromatic vinyl compound can be calculated | required by 1H-NMR measurement.

  The content of the monomer unit derived from the conjugated diene compound is preferably 50% by weight to 90% by weight, and more preferably 60% by weight to 90% by weight. However, the total amount of the copolymer having monomer units derived from an aromatic vinyl compound and monomer units derived from a conjugated diene compound is 100% by weight. The content of the monomer unit derived from the conjugated diene compound can be determined by 1H-NMR measurement.

The hydrogenation rate of the hydrogenated product of the copolymer (3) is preferably 80% or more, and more preferably 90% or more. However, the amount of the double bond of the monomer unit derived from the conjugated diene compound in the copolymer (3) before hydrogenation is 100%.
As a copolymer (3) having a monomer unit derived from an aromatic vinyl compound and a monomer unit derived from a conjugated diene compound, an aromatic vinyl compound-conjugated diene compound-aromatic vinyl compound polymer is used. Hydrogenated products are preferred.

  As a manufacturing method of a copolymer (3), the method described in Japanese Patent Publication No.40-23798 is mentioned, for example. Further, as a method of hydrogenating a copolymer having a monomer unit derived from an aromatic vinyl compound and a monomer unit derived from a conjugated diene compound, for example, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43 And the methods described in JP-A-6636, JP-A-59-133203, and JP-A-60-79005. As a copolymer having a monomer unit derived from an aromatic vinyl compound and a monomer unit derived from a conjugated diene compound, “KRATON-G” manufactured by Kraton Polymer, “Septon” manufactured by Kuraray Co., Ltd., Asahi Kasei Chemicals Commercial products such as “Tuftec” manufactured by KK may be used.

<Resin composition>
The resin composition of the present invention comprises the polymer (1),
Polystyrene (2),
Containing a copolymer (3) having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound,
When the total amount of the polymer (1), polystyrene (2) and the copolymer (3) is 100% by weight, the content of the polymer (1) is 10% by weight or more and 90% by weight or less. The resin composition has a polystyrene (2) content of 10 wt% or more and 90 wt% or less and a copolymer (3) content of 0.1 wt% or more and 50 wt% or less.
The polymer (1) may be composed of two or more types of polymers, the polystyrene (2) may be composed of two or more types of polymers, and the copolymer (3) is composed of two or more types of polymers. It may consist of a unity.

  From the viewpoint of moldability, the resin composition of the present invention has a melt flow rate (MFR) measured in accordance with JIS K7210 at 230 ° C. and a load of 2.16 kgf of 0.1 g / 10 min or more and 30 g. / 10 minutes or less is preferable.

  The resin composition of the present invention preferably has a gel fraction of 20% or more, more preferably 40% or more, still more preferably 60% or more, and most preferably 70% or more. The gel fraction indicates the degree of crosslinking of the crosslinked polymer, and the resin composition has a high gel fraction, which means that the polymer contained in the resin composition has more crosslinked structure. It means that a stronger network structure is formed. When the gel fraction of the resin composition is high, the resin composition has high shape retention and is not easily deformed.

In addition, a gel fraction is calculated | required by the method described below. An empty mesh bag made of about 500 mg of the polymer constituting the resin composition (corresponding to the weight of the sample to be measured) and a wire mesh (mesh opening: 400 mesh) is weighed. Net cage and xylene encapsulating a polymer (Kanto Chemical Co., Ltd. deer special grade or equivalent thereof: o-, m-, p-xylene and ethylbenzene mixture, total weight of o-, m-, p-xylene is 85 (50% by weight or more) 50 mL is introduced into a 100 mL test tube and subjected to heat extraction at 110 ° C. for 6 hours. After extraction, the net residue containing the extraction residue is taken out from the test tube, dried under reduced pressure at 80 ° C. for 8 hours in a vacuum dryer, and the net residue containing the extraction residue after drying is weighed. The gel weight is calculated from the difference in weight between the net with extraction residue after drying and the empty net with an extraction residue. The gel fraction (% by weight) is calculated based on the following formula.
Gel fraction = (gel weight / measured sample weight) × 100

The resin composition of the present invention comprises an inorganic filler, an organic filler, an antioxidant, a weathering stabilizer, an ultraviolet absorber, a heat stabilizer, a light stabilizer, an antistatic agent, a crystal nucleating agent, a pigment, an adsorbent, and a metal chloride. Additives such as products, hydrotalcite, aluminates, lubricants, and silicone compounds.
When the resin composition of the present invention contains an additive, the polymer (the polymer (1), polystyrene (2), copolymer (3), or other polymer) contained in the resin composition The additive may be blended in advance with one or more raw materials used in the production of (), or may be blended after the polymer contained in the resin composition is manufactured. When the additive is blended after the polymer contained in the resin composition is produced, the additive can be blended while melt-kneading the polymer. For example, when producing a resin composition while melt-kneading the polymer (1), polystyrene (2) and copolymer (3), and other polymers used as necessary, an additive Can be blended.

  The amount of these additives is preferably 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, based on 100 parts by weight of the resin composition of the present invention. More preferably, the amount is 0.01 parts by weight or more and 1 part by weight or less.

Examples of the inorganic filler include talc, calcium carbonate, and calcined kaolin.
Examples of the organic filler include fiber, wood powder, and cellulose powder.
Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, a lactone-based antioxidant, and a vitamin-based antioxidant.
Examples of the UV absorber include benzotriazole UV absorbers, tridiamine UV absorbers, anilide UV absorbers, and benzophenone UV absorbers.
Examples of the light stabilizer include hindered amine light stabilizers and benzoate light stabilizers.
Examples of the pigment include titanium dioxide and carbon black.
Examples of the adsorbent include metal oxides such as zinc oxide and magnesium oxide.
Examples of the metal chloride include iron chloride and calcium chloride.
Examples of the lubricant include fatty acids, higher alcohols, aliphatic amides, and aliphatic esters.

  The resin composition of the present invention and the molded body of the resin composition can be used as a heat storage material. The resin composition of this invention and the molded object of this resin composition can be used as a heat insulating material using the thermal storage performance.

  Since the heat storage material containing the resin composition of the present invention is excellent in moldability and shape retention, the shape thereof is arbitrary. For example, a spherical shape, a rectangular shape (cube shape), a bead shape (bead shape), a cylindrical shape ( Pellet form), powder form, rod form (stick form), needle form, fiber form (fiber form), strand form, thread form, string form, rope form, rope form, plate form, sheet form, film form (film form), Examples include a woven fabric shape, a nonwoven fabric shape, a box shape (capsule shape), a foam shape, and an arbitrary three-dimensional shape, and the shape can be selected according to the purpose of use.

  In addition, the heat storage material that is spherical, square (cube), beaded (bead), cylindrical (pellet), or powder, the resin composition of the present invention is the resin composition of the present invention. A core-shell structure covered with a different material or a material different from the resin composition of the present invention may form a core-shell structure covered with the resin composition of the present invention. In addition, the material different from the resin composition of the present invention is a polymer, a metal, and an inorganic substance other than the metal different from the resin composition of the present invention.

  The heat storage material in the form of a rod (stick), needle, fiber (fiber), strand, thread, string, rope, or rope is the resin composition of the present invention. A core-sheath structure covered with a material different from the composition, or a material different from the resin composition of the present invention may form a core-sheath structure covered with the resin composition of the present invention.

  Further, the heat storage material in the form of a plate, sheet, film (film), woven fabric, non-woven fabric, or box (capsule) is double-sided or single-sided depending on the material different from the resin composition of the present invention. Or a core-sheath structure in which a material different from the resin composition of the present invention is covered with the resin composition of the present invention.

  The heat storage material in the form of a foam has a core-shell structure, a core-sheath structure, or a laminated structure with the heat storage material having a shape different from the foam shape, or a material different from the resin composition of the present invention. It may be formed.

  Further, the heat storage material can be formed into an arbitrary three-dimensional shape by, for example, extrusion molding, injection molding, vacuum molding, blow molding, or rolling molding, and each is a multilayer with a material different from the resin composition of the present invention. Molding can also be performed.

<Fiber containing resin composition>
The heat storage material is a fiber obtained by spinning the resin composition of the present invention (hereinafter sometimes referred to as the resin composition (A)), or a fabric / fabric made of the fiber, a nonwoven fabric and a fiber made of cotton. It may be.

  In the resin composition (A), the phase composed of the polymer (1) and the phase composed of polystyrene (2) may form a morphology such as a sea-island structure, a cylinder structure, a lamellar structure, and a bicontinuous structure.

  The cross-sectional shape of the fiber containing the resin composition (A) may be a circular cross-section, an irregular cross-section such as a polygonal or multi-leaf shape, or a hollow cross-section.

  The single yarn fineness of the fiber containing the resin composition (A) is not particularly limited, but is preferably 1 dtex or more from the viewpoint of easy fiberization, and preferably 20 dtex or less from the viewpoint of fiber flexibility.

  Examples of the method for producing the fiber containing the resin composition (A) include a dry spinning method, a wet spinning method, and a melt spinning method, and a melt spinning method is preferable. The general spinning method includes two steps, a spinning step and a drawing step, using a chip containing a resin composition as a raw material. As a spinning method suitably used for the production method of the fiber containing the resin composition (A), a continuous polymerization spinning method in which the resin composition is continuously spun from the resin composition production step without forming a chip, a spinning step and stretching POY-DTY to obtain a drawn yarn (DTY) in a false twisting process via a direct spinning drawing method (spin draw method) in which the step is performed in one step, a high speed spinning method that does not require a drawing step, and a semi-drawn yarn (POY) Or a spunbond method. These methods are more streamlined than the general spinning method.

  The fiber containing the resin composition (A) may be a composite fiber. The composite fiber refers to a fiber in which two or more kinds of fibers composed of different components are joined in a single yarn. Examples of the composite fiber include a core-sheath composite fiber, a bonded composite fiber, a split composite fiber, and a sea-island composite fiber.

  The single yarn fineness of the composite fiber containing the resin composition (A) is not particularly limited, but is preferably 1 dtex or more from the viewpoint of easy fiberization, and preferably 20 dtex or less from the viewpoint of fiber flexibility.

  As the structure of the core-sheath type composite fiber, the resin composition (A) is a core-sheath structure in which the resin composition (A) is covered with a different material, or the material different from the resin composition (A) is the resin composition. The core-sheath structure covered with the thing (A) etc. are mentioned, Preferably, it is the core-sheath structure where the resin composition (A) was covered with the material different from the resin composition (A). The material different from the resin composition (A) is preferably polypropylene (PP), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyamide 6 (PA6), polyamide 66 (PA66).

  As the composite fiber having a core-sheath structure in which the resin composition (A) is covered with a material different from that of the resin composition (A), the area ratio of the core portion in the fiber radial direction cross section is 10% to 90%. Bicomponent fibers are preferred. From the viewpoint of the temperature adjusting function, the area ratio of the core is preferably 10% or more, and from the viewpoint of fiber strength, the area ratio of the core is preferably 90% or less. When the core includes polypropylene, the area ratio of the core is preferably 20% to 50% from the viewpoint of dyeability of the entire fiber.

  The bonded composite fiber is generally crimped due to a difference in shrinkage, etc., but when the composite fiber is crimped in a spiral shape, the resin composition (A) may be inside the spiral, The material different from the composition (A) may be inside the helix, and preferably a bonded composite fiber in which the resin composition (A) is inside the helix. The material different from the resin composition (A) is preferably polypropylene (PP), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyamide 6 (PA6), polyamide 66 (PA66).

  A split type composite fiber is split and opened by chemical treatment to obtain ultrafine fibers. When the split type composite fiber is composed of a central radial fiber and a plurality of surrounding wedge-shaped fibers, the resin composition (A) may be a central radial fiber, and a material different from the resin composition (A) is the center. The resin composition (A) is preferably a split type composite fiber that is a central radial fiber. The material different from the resin composition (A) is preferably polypropylene (PP), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyamide 6 (PA6), polyamide 66 (PA66).

  As for the sea-island type composite fiber, the sea part fiber is removed by chemical treatment to obtain an ultrafine fiber composed of a plurality of island part fibers. The resin composition (A) may be a sea part fiber, and the material different from the resin composition (A) may be a sea part fiber. Preferably, a sea island type in which the resin composition (A) is a sea part fiber. It is a composite fiber. The material different from the resin composition (A) is preferably polypropylene (PP), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyamide 6 (PA6), polyamide 66 (PA66).

  Examples of the form of the fiber containing the resin composition (A) include long fibers (multifilament, monofilament), short fibers (staple), and the like. Long fibers (multifilaments, monofilaments) may be used as they are, or may be formed into false twisted yarns by false twisting, or mixed yarns by air mixed fiber or the like. The short fibers (staples) may be used as they are, or may be spun by spinning, or may be blended by blending. It may be a core spun yarn in which short fibers are combined with long fibers, and may be a twisted yarn, a twisted yarn, or a covering yarn by twisting.

  Fibers containing the resin composition (A) are antioxidants, pigments, dyes, antibacterial agents, deodorants, antistatic agents, flame retardants, inert fine particles, light absorption heating materials, moisture absorption heating materials, far infrared heating materials. In addition, other additives may be contained. The additive can be added during spinning or after spinning.

  The light-absorbing heat-generating fiber containing the resin composition (A) and the light-absorbing heat-generating material allows the light-absorbing heat-generating material such as zirconium carbide, which absorbs a specific wavelength of sunlight and converts it into heat energy, to adhere to the inside and the surface of the fiber. Fiber. The cloth made of the light-absorbing heat-generating fiber can raise the temperature of the cloth surface that is in contact with the sun as compared with the cloth made of the fiber not containing the light-absorbing heat-generating material.

  The hygroscopic exothermic fiber including the resin composition (A) and the hygroscopic exothermic material is a fiber that generates adsorption heat at the time of moisture absorption, and is a fiber that releases moisture in a low humidity environment and has an effect of controlling the ambient temperature and humidity. is there.

  The far-infrared processed fiber containing the resin composition (A) and the far-infrared radiation material is a fiber in which ceramics having high far-infrared radiation are fixed to the inside and the surface of the fiber, and has a heat retaining effect by far-infrared radiation. .

  The fabric / fabric composed of fibers containing the resin composition (A) may be woven fabric, knitted fabric, or nonwoven fabric. Examples of the weave structure include plain weave (plain), twill (twill), satin weave (satin) and their changed structures, dobby, jacquard and the like. Examples of the knitting structure include a weft knitting, a warp knitting, and a change organization thereof.

  There are no particular limitations on the basis weight, gauge, etc. of the fabric / fabric comprising the fiber containing the resin composition (A).

  The fabric / fabric composed of the fiber containing the resin composition (A) may be composed of only the fiber containing the resin composition (A), or may be used by weaving or knitting with other fibers. Other fibers include carbon fibers, inorganic fibers, inorganic fibers such as metal fibers, refined fibers such as lyocell, regenerated fibers such as rayon, cupra, and polynosic, semi-synthetic fibers such as acetate, triacetate, and promix, acrylic, acrylic Fibers, vinylon, vinylidene, polyvinyl chloride, polyethylene, polyclar, aramid, polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyamide 66 (PA66), synthetic fibers such as urethane, cotton, cellulose fibers , Plant fibers such as hemp (flax, linseed, cannabis, jute), natural fibers that are animal fibers such as wool, wool, animal hair (angola, cashmere, mohair, alpaca, camel, etc.), silk, down, feather, etc. And feathers. The use ratio of the fiber containing the resin composition (A) is not particularly limited, but is preferably 20% by weight to 100% by weight.

  The nonwoven fabric made of the fiber containing the resin composition (A) may contain a heat-bonding binder fiber. The heat-sealable binder fiber is preferably a composite fiber such as a core-sheath type or a bonded type made of a material having a different melting point from the resin composition (A). The material having a melting point different from that of the resin composition (A) is preferably polypropylene (PP), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyamide 6 (PA6). Polyamide 66 (PA66).

  When using this heat-fusible binder fiber, it is preferable that the content shall be 5 to 20 weight% in the whole fiber of a nonwoven fabric.

The nonwoven fabric composed of fibers containing the resin composition (A) preferably has a basis weight of 100 g / m ² or less and a thickness of 5 mm or less, and a basis weight of 60 g / m ² from the viewpoint of lightness, soft touch, and fashionability of clothing. More preferably, it is m ² or less.

  The manufacturing method of the nonwoven fabric which consists of a fiber containing a resin composition (A) normally contains the formation process of a web, and the bonding process of a web. Examples of the web forming process include a dry method, a wet method, a spunbond method, a melt blown method, an airlaid method, and the web bonding process includes a chemical bond method, a thermal bond method, a needle punch method, a hydroentanglement method, and the like. Is mentioned.

  Since the fabric / fabric made of fibers containing the resin composition (A) has a temperature control function, the fabric / fabric basis weight can be reduced and the thickness can be reduced. Will not be damaged. In addition, since the fabric / fabric made of fibers containing the resin composition (A) contains a polymer-type latent heat storage material, the fabric / cloth made of fibers containing a low-molecular type latent heat storage material enclosed in microcapsules. Compared to, it has excellent durability.

<Foam>
The foam containing the resin composition of the present invention comprises a resin composition (hereinafter referred to as resin composition (B)) containing the polymer (1), polystyrene (2), the copolymer (3) and a foaming agent. May be obtained by foaming.
Examples of the foaming agent include physical foaming agents and pyrolytic foaming agents. A plurality of foaming agents may be used in combination.

  Examples of the physical foaming agent include air, oxygen, nitrogen, carbon dioxide, ethane, propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, cyclohexane, heptane, ethylene, propylene, water, petroleum Examples include ether, methyl chloride, ethyl chloride, monochlorotrifluoromethane, dichlorodifluoromethane, dichlorotetrafluoroethane, among which carbon dioxide, nitrogen, n-butane, isobutane, n-pentane or isopentane is economical and safe. From the viewpoint of sex.

  Examples of the pyrolytic foaming agent include inorganic foaming agents such as sodium carbonate, azodicarbonamide, N, N-dinitropentamethylenetetramine, p, p′-oxybisbenzenesulfonylhydrazide, hydrazodicarbonamide, and the like. Among them, azodicarbonamide, sodium hydrogen carbonate, p, p'-oxybisbenzenesulfonyl hydrazide are preferable from the viewpoints of economy and safety, and a wide molding temperature range is used. Since a fine foam can be obtained, a foaming agent containing azodicarbonamide or sodium hydrogen carbonate is more preferable.

  When using a thermally decomposable foaming agent, a thermally decomposable foaming agent whose decomposition temperature is 120-240 degreeC is normally used. When a thermal decomposition type foaming agent having a decomposition temperature higher than 200 ° C. is used, it is preferable to lower the decomposition temperature to 200 ° C. or less by using a foaming aid in combination. As foaming aids, metal oxides such as zinc oxide and lead oxide; metal carbonates such as zinc carbonate; metal chlorides such as zinc chloride; urea; zinc stearate, lead stearate, dibasic lead stearate, Metal soap such as zinc laurate, zinc 2-ethylhexoate, and dibasic lead phthalate; Organotin compounds such as dibutyltin dilaurate and dibutyltin dimale; Tribasic lead sulfate, dibasic lead phosphite, basic Mention may be made of inorganic salts such as lead sulfite.

  As the pyrolyzable foaming agent, a master batch composed of a pyrolyzable foaming agent, a foaming aid and a resin can be used. Although the kind of resin used for a masterbatch is not specifically limited, The polymer contained in the resin composition or the said resin composition of this invention is preferable. The total amount of the pyrolyzable foaming agent and foaming aid contained in the masterbatch is usually 5 to 90% by weight when the resin contained in the masterbatch is 100% by weight.

  In order to obtain a foam having finer bubbles, the resin composition (B) preferably further contains a foam nucleating agent. Foam nucleating agents include talc, silica, mica, zeolite, calcium carbonate, calcium silicate, magnesium carbonate, aluminum hydroxide, barium sulfate, aluminosilicate, clay, quartz powder, diatomaceous earth; particle size of 100 μm consisting of polymethyl methacrylate and polystyrene The following organic polymer beads: organic acid metal salts such as calcium stearate, magnesium stearate, zinc stearate, sodium benzoate, calcium benzoate, aluminum benzoate; metal oxides such as magnesium oxide and zinc oxide, and the like Two or more types may be combined.

  In the resin composition (B), the amount of the foaming agent is appropriately set according to the type of foaming agent to be used and the foaming ratio of the foam to be produced, but the amount of the resin component contained in the resin composition (B). When the weight is 100 parts by weight, it is usually 1 to 100 parts by weight.

  The resin composition (B) may contain additives such as a heat stabilizer, a weather stabilizer, a pigment, a filler, a lubricant, an antistatic agent, and a flame retardant as necessary.

  The resin composition (B) is obtained by melt-kneading the polymer (1), polystyrene (2), the copolymer (3), a foaming agent, and other components blended as necessary. It is preferable. Examples of the melt kneading method include, for example, mixing the polymer (1), polystyrene (2), the copolymer (3), and a foaming agent with a mixing device such as a tumbler blender or a Henschel mixer, Examples thereof include a melt kneading method using an extruder or a multi-screw extruder, and a melt kneading method using a kneader such as a kneader or a Banbury mixer.

  A known method can be used for producing the foam, and extrusion foam molding, injection foam molding, pressure foam molding and the like are preferably used.

  When the foam of the present invention contains a crosslinked polymer (1), as a method for producing the foam, for example, the resin composition containing the polymer (α) and a foaming agent may be ionized. A step of producing a resin composition (α) containing the crosslinked polymer (1) and the foaming agent by irradiating with radiation or melt-kneading the crosslinked polymer (1) and the foaming agent; A method comprising heating a resin composition (α) to produce a foam (hereinafter referred to as method (A)), the polymer (α), a foaming agent, and organic peroxidation in a mold Or a resin composition (β) containing a crosslinked polymer (1) under pressure while heating the resin composition containing a polymer (1) and a foaming agent. A method (hereinafter referred to as method (B)) including a step of manufacturing and a step of manufacturing a foam by opening a mold. ). In addition, as a raw material of a resin composition ((alpha)) or a resin composition ((beta)), the said polystyrene (2) and the said copolymer (3) can be included.

The method (A) will be specifically described below.
Examples of the ionizing radiation used for irradiating the resin composition containing the polymer (α) and the foaming agent include ionizing radiation used for the production of the crosslinked polymer (1). Examples of the irradiation method and irradiation amount of ionizing radiation include the same methods and irradiation amounts described as the irradiation method and irradiation amount during the production of the crosslinked polymer (1).
The resin composition containing the polymer (α) and the foaming agent is usually irradiated with ionizing radiation after being formed into a desired shape at a temperature lower than the decomposition temperature of the foaming agent. For example, as a method of forming into a sheet, a method of forming into a sheet form with a calender roll, a method of forming into a sheet form with a press molding machine, and a method of forming into a sheet form by melt extrusion from a T die or an annular die are mentioned. It is done.
The melt-kneading of the crosslinked polymer (1) and the foaming agent is usually performed at a temperature lower than the decomposition temperature of the foaming agent.

  In the step of producing a foam by heating the resin composition (α), a known method for producing a resin foam can be applied as a method for producing a foam by heating, and vertical hot-air foaming can be applied. A method in which the resin composition (α) can be continuously heated and foamed, such as a method, a horizontal hot air foaming method, and a horizontal chemical liquid foaming method, is preferable. The heating temperature is a temperature equal to or higher than the decomposition temperature of the foaming agent, and preferably 5 to 50 ° C. higher than the decomposition temperature of the thermally decomposable foaming agent. Moreover, although heating time can be suitably selected according to the kind of foaming agent, quantity, etc., when heating with oven, it is 3 to 5 minutes normally.

The method (B) will be specifically described below.
As an organic peroxide, the organic peroxide which can be used for manufacture of the bridge | crosslinked polymer (1) is mentioned.

A resin composition to be pressurized while heating in a mold is a resin composition containing the polymer (α), a foaming agent, and an organic peroxide, or a crosslinked polymer (1). It is preferable that the resin composition containing the foam is melt-kneaded at a temperature lower than the decomposition temperature of the foaming agent and lower than the 1 minute half-life temperature of the organic peroxide.
The temperature at which the resin composition containing the polymer (α), the foaming agent, and the organic peroxide is heated in the mold is equal to or higher than the one-minute half-life temperature of the organic peroxide, and the foaming agent is decomposed. A temperature equal to or higher than the temperature is preferred.

In the step of opening the mold and producing the foam, it is preferable to open the mold after cooling the mold to 40 ° C. or more and 100 ° C. or less. The temperature of the mold when opening is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoint of increasing the melt viscosity of the resin composition (β) and promoting expansion during foaming. Further, from the viewpoint of suppressing gas escape during foaming, it is preferably 90 ° C. or lower, and more preferably 80 ° C. or lower.
However, since the temperature of the mold suitable for opening varies depending on the viscosity and melting point of the resin composition (β) and the size of the foam to be produced, it can be appropriately adjusted.

  Moreover, in order to raise the expansion ratio and intensity | strength of the foam containing the polymer (1) bridge | crosslinked, the resin composition containing the said polymer ((alpha)) and a foaming agent may contain a crosslinking adjuvant further. preferable. Examples of the crosslinking aid include a crosslinking aid used for the production of the crosslinked polymer (1). The amount of the crosslinking aid contained in the resin composition containing the polymer (α), the foaming agent and the crosslinking aid is 0.01 when the weight of the resin component contained in the resin composition is 100 parts by weight. It is preferable that it is -4.0 weight part, and it is more preferable that it is 0.05-2.0 weight part.

  The heat storage material containing the resin composition of the present invention is excellent in heat storage performance, molding processability, shape retention, and moisture permeability, and thus, for example, a product or a member thereof that directly or indirectly requires heat insulation / cooling performance. Can be suitably used.

  Examples of products or components for which heat insulation / cooling performance are required directly or indirectly include, for example, building materials, furniture, interior goods, bedding, bathroom materials, vehicles, air conditioning equipment, electrical appliances, heat insulation containers, clothing, daily necessities , Agricultural materials, fermentation systems, thermoelectric conversion systems, heat transfer media.

  Examples of the building material include floor materials, wall materials, wallpaper, ceiling materials, roof materials, floor heating systems, tatami mats, doors, fences, shutters, shoji screens, windows, and window frames. When using as a wall material, the use as an outer-layer heat insulating material or a filling heat insulating material is mentioned, for example, and the molded object of the resin composition of this invention can be constructed.

  When used as a flooring material, wall material, ceiling material, or roofing material, for example, in the form of a plate, a sheet, or a foam, in order to further reduce the fluctuation of the indoor space temperature against the fluctuation of the external environment temperature A laminate having the heat storage material, a heat insulating material made of a material different from the resin composition of the present invention, and a heat shielding material made of a material different from the resin composition of the present invention can be suitably used.

  Examples of the heat insulating material include polystyrene foam, polyurethane foam, acrylic resin foam, phenol resin foam, polyethylene resin foam, foam rubber, glass wool, rock wool, foam ceramic, vacuum heat insulating material, and composites thereof. The body is mentioned.

  Examples of the heat shielding material include an aluminum plate, an aluminum foil, an aluminum powder-containing paint, a ceramic powder paint, and a composite thereof.

  When used as a wall material, a ceiling material, or a roof material, in order to impart fire resistance, for example, from the plate-shaped, sheet-shaped or foam-shaped heat storage material, a material different from the resin composition of the present invention. The laminated body with the fire retardant which becomes the flame-retardant property, semi-incombustibility, or non-combustibility which becomes can be used suitably.

  Examples of the fireproofing material include concrete, gypsum, woody cement, calcium silicate, glass, metal, foamable fireproofing material, flame retardant-containing material, and composites thereof.

  When used as a member of a floor heating system, in order to efficiently use heat generated from a heating element such as a heating cable, a planar heater, and a hot water pipe for maintaining a room temperature, for example, a plate shape, a sheet shape, It is preferable to use a laminate having the foam-like heat storage material, a heat insulating material made of a material different from the resin composition of the present invention, and a sensible heat storage material made of a material different from the resin composition of the present invention. it can.

  Examples of the sensible heat storage material include concrete, mortar, concrete slab, and composites thereof.

  When used as a tatami member, in order to further reduce the fluctuation of the indoor space temperature with respect to the fluctuation of the external environment temperature, for example, the heat storage material in the form of a plate, sheet or foam, the resin composition of the present invention A laminate having a heat insulating material made of a material different from the product, a tatami board made of a material different from the resin composition of the present invention, and a tatami surface made of a material different from the resin composition of the present invention can be suitably used. Moreover, when using it for a tatami board material, the thermal storage tatami board which consists of a mixture of the said thermal storage material and wood fiber can be used suitably, and when using it for a tatami surface material, it is fibrous (fiber form) or a strand form. A heat storage tatami mat composed of heat storage fibers forming a core-sheath structure of a tatami mat surface composed of a material different from the heat storage material and the resin composition of the present invention can be suitably used.

  When used as a door member, fence member or shutter member, in order to further reduce fluctuations in the room temperature of the room partitioned by the door, fence or shutter, for example, plate-like, sheet-like or foam-like The heat storage material, a heat insulating material made of a material different from the resin composition of the present invention, and a laminate having a surface material made of a material different from the resin composition of the present invention can be suitably used.

  When used as a shoji member, for example, the heat storage material in the form of a foam or non-woven fabric is used in order to further reduce fluctuations in the room temperature of the room partitioned by the shoji and to provide a certain degree of light transmission. Or the laminated body which has the shoji paper which consists of a material different from the said heat storage material of a foam form or a nonwoven fabric form, and the resin composition of this invention can be used suitably.

  When used as a window member, in order to further reduce the fluctuation of the indoor space temperature with respect to the fluctuation of the external environment temperature, and to provide a certain degree of light transmittance, for example, in the form of foam or nonwoven fabric A laminate comprising the heat storage material and glass, polycarbonate, or polymethyl methacrylate can be suitably used.

  When used as a member of a window frame, in order to further reduce the fluctuation of the indoor space temperature with respect to the fluctuation of the external environment temperature, and to reduce the temperature difference of the window frame from the room temperature to prevent condensation, For example, a laminated body composed of the plate-like, sheet-like or foam-like heat storage material and a metal window frame or a resin window frame different from the resin composition of the present invention can be suitably used.

  As furniture, interior goods, and bedding, a partition board, a blind, a curtain, a carpet, a futon, and a mattress are mentioned, for example.

  When used as a member of a partition board, in order to further reduce fluctuations in the room temperature of the room partitioned by the partition board, for example, the plate-like, sheet-like or foam-like heat storage material, the resin composition of the present invention A laminate having a heat insulating material made of a material different from the above and a surface material made of a material different from the resin composition of the present invention can be suitably used.

  When used as a blind member, in order to further reduce the fluctuation of the indoor space temperature with respect to the fluctuation of the external environment temperature, and to provide a light shielding performance, for example, the plate-like or sheet-like heat storage material and A laminate having a heat shield made of a material different from the resin composition of the present invention can be suitably used. For example, if the structure of the blinds is composed of a heat shield surface and a heat storage surface as described above, use the heat shield surface outside during the summer, and use the heat storage surface outside during the day in winter and heat storage at night. By reversing the surface inward, the amount of solar heat flowing into the building can be controlled according to the season and time zone, so the power consumption of the air conditioning equipment can be reduced.

  When used as a curtain, carpet or futon, for example, from a material different from the heat storage material in the form of fibers (fibers) or strands and the resin composition of the present invention in order to give an arbitrary texture or touch. A heat storage woven fabric or a heat storage non-woven fabric made of heat storage fibers having a core-sheath structure with the fiber material to be formed can be suitably used.

  When used as a carpet, for example, the heat storage material in the form of a plate, a sheet or a foam, and fibers made of a material different from the resin composition of the present invention are used in order to give an arbitrary texture and feel. A laminate having a woven fabric or a nonwoven fabric can be suitably used.

  When used as a mattress, for example, the heat storage material in the form of a foam can be suitably used in order to impart flexibility.

  Examples of the bathroom material include a bathtub material, a bath lid material, a bathroom floor material, a bathroom wall material, and a bathroom ceiling material.

  When used as a bathtub material or a bath lid material, for example, the heat storage material in the form of a plate, sheet or foam in order to further reduce fluctuations in hot water temperature in the bathtub with respect to fluctuations in the bathroom temperature. A laminate having a heat insulating material made of a material different from the resin composition of the present invention and a surface material made of a material different from the resin composition of the present invention can be suitably used.

  When used as a bathroom flooring material, bathroom wall material, or bathroom ceiling material, for example, in the form of a plate, a sheet, or a foam, in order to further reduce fluctuations in bathroom temperature against fluctuations in external environment temperature A laminate having a heat storage material, a heat insulating material made of a material different from the resin composition of the present invention, and a heat shielding material made of a material different from the resin composition of the present invention can be suitably used.

  Examples of the vehicle member include an engine warm-up system, a gasoline evaporation loss prevention device (canister), an in-vehicle air conditioner, an interior material, a cold vehicle container member, and a warm vehicle container member.

  Examples of air conditioning equipment members include a heat storage material for a housing heat storage air conditioning system, a heat storage tank member for a water heat storage air conditioning system, a heat storage tank member for an ice heat storage air conditioning system, a heat medium piping material or its heat retaining material, and a refrigerant. Examples thereof include piping materials or heat insulating materials thereof, and duct materials for heat exchange type ventilation systems.

As an electrical appliance, for example,
TV, Blu-ray recorder player, DVD recorder player, monitor, display, projector, rear projection TV, component, radio and cassette player, digital camera, digital video camera, mobile phone, smartphone, notebook computer, desktop computer, tablet PC, PDA, printer, 3D Electronic devices such as printers, scanners, home game machines, portable game machines, storage batteries for electronic devices, and transformers for electronic devices,
Electric heater, fan heater, dehumidifier, humidifier, hot carpet, kotatsu, electric blanket, electric rug, electric anchor, heated toilet seat, hot water washing toilet seat, iron, trouser press, duvet dryer, clothes dryer, hair dryer, Heated household appliances such as curling irons, thermal massagers, thermal therapy devices, dishwashers, dish dryers, and dry garbage processing machines
IH cooking heater, hot plate, microwave oven, microwave oven, rice cooker, rice cake machine, home bakery, toaster, electronic fermenter, electric kettle, electric kettle, coffee maker, etc.
Cooking home appliances that generate frictional heat such as mixers, food processors, rice mills, refrigeration / freezers, constant temperature and humidity cold storage, milk cold storage, brown rice cold storage, vegetable cold storage, cold rice bran, frozen refrigerated showcase, prefabricated Examples include a type of cold storage, a prefabricated refrigerated showcase, a hot and cold distribution car, a wine cellar, a food vending machine, and a bento warming cabinet.

  When used as a member of an electronic device, for example, the plate-like or sheet-like heat storage material can be suitably used to protect the electronic component from heat generated from the electronic component constituting the electronic device. In particular, in the case where a large amount of heat is generated locally, such as highly integrated electronic parts, in order to efficiently absorb the heat generated from the heating element to the plate-shaped or sheet-shaped heat storage material, for example, a plate A laminate having a high thermal conductive material made of a material different from the heat storage material in the form of a sheet or a sheet and the resin composition of the present invention can be suitably used.

  Examples of the high thermal conductive material include carbon nanotubes, boron nitride nanotubes, graphite, copper, aluminum, boron nitride, aluminum nitride, aluminum oxide, magnesium oxide, and composites thereof.

  When used as a member of an electronic device used in a state in contact with the human body, in order to suppress heat generated from electronic components constituting the electronic device from being conducted to the human body through the housing constituting the electronic device, For example, a laminate composed of the plate-shaped or sheet-shaped heat storage material and the housing material can be suitably used.

  When used as a member of a heating-type household appliance, in order to protect other parts constituting the heating-type household appliance from heat generated from a heating device constituting the heating-type household appliance, for example, a plate-like or sheet-like The said heat storage material can be used suitably. In addition, in order to improve heat insulation performance and reduce power consumption, for example, a plate-like, sheet-like or foam-like heat storage material and a laminate having a heat insulating material made of a material different from the resin composition of the present invention are suitable. Can be used.

  When used as a member of a heating type cooking appliance, in order to protect other parts constituting the heating type cooking appliance from heat generated from a heating device constituting the heating type cooking appliance, for example, a plate shape or a sheet shape The said heat storage material can be used suitably. In addition, in order to improve heat insulation performance and reduce power consumption, for example, a plate-like, sheet-like or foam-like heat storage material and a laminate having a heat insulating material made of a material different from the resin composition of the present invention are suitable. Can be used.

  When used as a member of cooking appliances that generate frictional heat, in order to protect food from frictional heat, for example, the plate-like or sheet-like heat storage material and high heat made of a material different from the resin composition of the present invention A laminate having a conductor can be preferably used.

  When used as a member of a heat insulated cooler with a power source, for example, the plate-like, sheet-like or foam-like heat storage material, the present invention, in order to further reduce the fluctuation of the internal temperature with respect to the fluctuation of the external environment temperature A laminate having a heat insulating material made of a material different from that of the resin composition and a heat shielding material made of a material different from the resin composition of the present invention can be suitably used.

  Examples of the heat and cold containers include a heat and cold container for transporting and storing specimens and organs, a heat and cold container for transporting and storing pharmaceuticals and chemical substances, and a heat and cold container for transporting and storing foods. Further, when used as a member of a heat and cold insulation container, in order to further reduce fluctuations in internal temperature with respect to fluctuations in external environment temperature, for example, the heat storage material in the form of a plate, sheet or foam, A laminate having a heat insulating material made of a material different from the resin composition and a heat shield made of a material different from the resin composition of the present invention can be suitably used.

  Examples of the clothing include sleeping clothes, winter clothes, gloves, socks, sportswear, wet suits, dry suits, heat-resistant protective clothes, and fire-resistant protective clothes. In addition, when used for clothing, in order to keep the body temperature constant and to give an arbitrary touch feeling, for example, the heat storage material in the form of fibers (fibers) or strands and a material different from the resin composition of the present invention are used. A heat storage woven fabric or a heat storage non-woven fabric made of heat storage fibers having a core-sheath structure with the fiber material to be formed can be suitably used.

  When used for wet suits or dry suits, in order to further reduce fluctuations in body temperature with respect to cold water, for example, the plate-shaped or sheet-shaped heat storage material, the heat storage woven fabric or the heat storage nonwoven fabric, and the A laminate having a heat insulating material made of a material different from that of the resin composition can be suitably used.

  When used in heat-resistant protective clothing or fire-resistant protective clothing, in order to further reduce fluctuations in body temperature against a heating element or flame, for example, the plate-shaped or sheet-shaped thermal storage material, the thermal storage fabric, or the thermal storage A laminate having a non-woven fabric, a heat insulating material made of a material different from the resin composition of the present invention, and a heat shield made of a material different from the resin composition of the present invention can be suitably used.

  Examples of daily necessities include tableware, lunch boxes, water bottles, thermos bottles, scallops, hot water bottles, cold insulation materials, and microwave oven type heat insulation materials.

  When used as a member of tableware or lunch box, in order to further reduce fluctuations in food temperature with respect to the external environment temperature, for example, the heat storage material in the form of a plate, sheet or foam, and the resin of the present invention You may use as a laminated body which has the heat insulating material which consists of a material different from a composition.

  Examples of fermentation systems that ferment organic waste such as business or household waste, sludge, livestock excrement, livestock and fishery residues, and vegetation to produce compost and biogas include bio-type garbage A processing machine, a fermenter for compost production, and a fermenter for biogas production may be mentioned. When used as the fermentation system, in order to further reduce the temperature fluctuation from the temperature suitable for the fermentation of the temperature in the tank with respect to the fluctuation of the external environment temperature, for example, the plate shape, the sheet shape or the foam shape A laminate having a heat storage material and a heat insulating material made of a material different from the resin composition of the present invention can be suitably used.

  Agricultural materials include, for example, greenhouse films, agricultural heat insulation sheets, irrigation hoses and pipes, and nursery farming electric mats. When used as an agricultural material, for example, in order to further reduce the temperature fluctuation from the temperature suitable for the growth of the crop, the ambient temperature of the crop with respect to the fluctuation of the external environment temperature, for example, in the form of a plate, sheet or foam The laminated body which has the heat insulating material which consists of a material different from the said heat storage material and the resin composition of this invention can be used suitably.

  Hereinafter, the present invention will be described in more detail by way of examples and comparative examples.

[I] The number of structural units (A) derived from ethylene contained in the polymer, the structural unit (B) represented by the above formula (1), and the structural unit (C) represented by the above formula (2) (unit: %)
Using a nuclear magnetic resonance spectrometer (NMR), a nuclear magnetic resonance spectrum (hereinafter referred to as NMR spectrum) was measured under the following measurement conditions.

<Measurement conditions for carbon nuclear magnetic resonance ( ¹³ C-NMR)>
Equipment: AVANCE III 600HD manufactured by Bruker BioSpin Corporation
Measurement probe: 10 mm cryoprobe Measurement solvent: 1,2-dichlorobenzene / 1,1,2,2-tetrachloroethane-d ₂ = 85/15 (volume ratio) mixed solution Sample concentration: 100 mg / mL
Measurement temperature: 135 ° C
Measurement method: proton decoupling method Integration number: 256 times Pulse width: 45 degrees Pulse repetition time: 4 seconds Measurement standard: tetramethylsilane

<Number of structural units derived from ethylene (A ₁ ) and structural units derived from methyl acrylate (C ₁ ) contained in the ethylene-methyl acrylate copolymer> (unit:%)
About the ¹³ C-NMR spectrum of the ethylene-methyl acrylate copolymer obtained according to the above ¹³ C-NMR measurement conditions, an integral value in the following a ₁ , b ₁ , c ₁ , d ₁ and e ₁ ranges is obtained. From the content (number) of three types of dyads (EE, EA, AA) obtained from the following formula, the structural unit derived from ethylene (A ₁ ) and the structural unit derived from methyl acrylate (C ₁ ) Numbers were calculated. Note that EE is ethylene-ethylene dyad, EA is ethylene-methyl acrylate dyad, and AA is methyl acrylate-methyl acrylate dyad.

a ₁ : 28.1-30.5 ppm
b ₁ : 31.9-32.6 ppm
c ₁ : 41.7 ppm
d ₁ : 43.1-44.2 ppm
e ₁ : 45.0-46.5 ppm

_{EE = a 1/4 + b} 1/2
EA = e ₁
AA = c ₁ + d ₁

Number of structural units (A ₁ ) = 100−Number of structural units (C ₁ ) Number of structural units (C ₁ ) = 100 × (EA / 2 + AA) / (EE + EA + AA)

<Conversion rate (X ₁ ) of structural unit (C ₁ ) derived from methyl acrylate to structural unit (B ₂ ) represented by formula ( ₁ )> (unit:%)
An ethylene-methyl acrylate copolymer and a long-chain alkyl alcohol are reacted to form a structural unit derived from ethylene (A ₂ ), a structural unit represented by formula (1) (B ₂ ), and a methyl acrylate. in the example was obtained _{(C 2)} from become polymer, the ¹³ C-NMR spectrum of the polymer obtained according to ¹³ C NMR measurement conditions described above, the following _{f 1} and _{g 1} ranging integral value Asked. Next, from the following formula, the structural unit (C ₁ ) derived from methyl acrylate contained in the ethylene-methyl acrylate copolymer was converted to the structural unit (B ₂ ) represented by the formula (1) of the polymer. Conversion (X ₁ ) was calculated.

f ₁ : 50.6-51.1 ppm
g ₁ : 63.9-64.8 ppm

Conversion rate (X ₁ ) = 100 × g ₁ / (f ₁ + g ₁ )

<Contained in the polymer, the structural units _(A 2) derived from ethylene, the constitutional unit _(B 2) represented by the formula (1), the number of structural units derived from methyl acrylate _{(C 2)>} (Unit:% )
Contained in the polymer, the number of constituent units derived from ethylene (A _2), the structural unit represented by the formula ₍₁₎ (B _2), the constitutional unit (C ₂₎ derived from methyl acrylate, each of the following formula Calculated from
Number of structural units (A ₂ ) contained in polymer = number of structural units (A ₁ ) contained in ethylene-methyl acrylate copolymer Number of structural units (B ₂ ) contained in polymer = (ethylene-methyl) Number of structural units (C ₁ ) contained in the acrylate copolymer) × conversion rate (X ₁ ) / 100
Number of structural units (C ₂ ) contained in polymer = (number of structural units (C ₁ ) contained in ethylene-methyl acrylate copolymer) − (number of structural units (B ₂ ) contained in polymer)
The number of structural units (A ₂ ), the number of structural units (B ₂ ), and the number of structural units (C ₂ ) thus obtained are structural units derived from ethylene contained in the polymer ( A) corresponds to the number (unit:%) of the structural unit (B) represented by the above formula (1) and the structural unit (C) represented by the above formula (2).

[II] Content of unreacted compound having an alkyl group having 14 to 30 carbon atoms (unit:% by weight)
In “Production of Polymer” in each Example, the product obtained is a mixture of the polymer and a compound having an unreacted alkyl group having 14 to 30 carbon atoms. The content of the compound having an unreacted alkyl group having 14 to 30 carbon atoms contained in the product was measured by a gas chromatograph (GC) by the following method. The content of the unreacted compound is a value when the total weight of the obtained polymer and the unreacted compound is 100% by weight.
[GC measurement conditions]
GC equipment: Shimadzu GC2014
Column: DB-5MS (60 m, 0.25 mmφ, 1.0 μm)
Column temperature: The temperature of the column maintained at 40 ° C. is increased to 300 ° C. at a rate of 10 ° C./minute, and then maintained at 300 ° C. for 40 minutes. Vaporization chamber / detector temperature: 300 ° C./300° C. (FID)
Carrier gas: Helium pressure: 220 kPa
Total flow rate: 17.0 mL / min Column flow rate: 1.99 mL / min purge flow rate: 3.0 mL / min Line speed: 31.8 cm / sec injection method / split ratio: split injection / 6: 1
Injection volume: 1 μL
Sample preparation method: 8 mg / mL (o-dichlorobenzene solution)
(1) Calibration curve creation [solution preparation]
Weigh 5 mg of the sample in a 9 mL vial tube, weigh 100 mg of n-tridecane as an internal standard substance, add 6 mL of o-dichlorobenzene as a solvent, completely dissolve the sample, and prepare a standard solution for preparing a calibration curve. Obtained. Two more standard solutions were prepared in the same manner as described above except that the amount of the sample was changed to 25 mg and 50 mg.
[GC measurement]
Measure the standard solution for creating a calibration curve under the GC measurement conditions described in the previous section, and create a calibration curve with the vertical axis representing the GC area ratio between the standard and the internal standard, and the horizontal axis representing the weight ratio between the standard and the internal standard. The slope a of the calibration curve was determined.
(2) Content measurement of measurement object (compound having an unreacted alkyl group having 14 to 30 carbon atoms) in a sample (product) [solution preparation]
50 mg of sample and 100 mg of n-tridecane were weighed in a 9 mL vial tube, 6 mL of o-dichlorobenzene was added, and the sample was completely dissolved at 80 ° C. to obtain a sample solution.
[GC measurement]
The sample solution was measured in the previous section of the GC measurement conditions, the content P _S of the measuring object in the sample was calculated according to the following equation.
P _S : Content of measurement object in sample (% by weight)
W _S : Weight of sample (mg)
W _IS : Weight of internal standard substance (IS) (mg)
A _S : Peak area count number of measurement object A _IS : Peak area count number of internal standard substance (IS) a: Slope of calibration curve of measurement object

[III] Method for evaluating physical properties of polymer (1) Melting peak temperature (T _m , unit: ° C.) Melting enthalpy (ΔH, unit: J / g) observed within a temperature range of 10 ° C. or more and less than 60 ° C.
Using a differential scanning calorimeter (TA Instruments, DSC Q100), under an atmosphere of nitrogen, an aluminum pan containing about 5 mg of sample was held at (1) 150 ° C. for 5 minutes, and then (2) 5 ° C. / The temperature is decreased from 150 ° C. to −50 ° C. at a rate of minutes, then (3) held at −50 ° C. for 5 minutes, and then (4) the temperature is increased from −50 ° C. to about 150 ° C. at a rate of 5 ° C./min. did. The differential scanning calorimetry curve obtained by calorimetry in step (4) was taken as the melting curve. The melting curve was analyzed by a method according to JIS K7121-1987 to determine the melting peak temperature.
The melting enthalpy ΔH (J / g) was determined by analyzing a portion within the temperature range of 10 ° C. or more and less than 60 ° C. of the melting curve by a method based on JIS K7122-1987.

(2) Ratio A defined by formula (I) (unit: none)
By gel permeation chromatography (GPC method) using a device equipped with a light scattering detector and a viscosity detector, the absolute molecular weights and inherent properties of the polymer and the polyethylene reference material 1475a (manufactured by National Institute of Standards and Technology) The viscosity was measured.
GPC equipment: Tosoh HLC-8121GPC / HT
Light scattering detector: Precision Detectors PD2040
Differential pressure viscometer: Viscotek H502
GPC column: Tosoh GMHHR-H (S) HT x 3 sample solution concentration: 2 mg / mL
Injection volume: 0.3 mL
Measurement temperature: 155 ° C
Dissolution condition: 145 ° C., 2 hours
Mobile phase: Orthodichlorobenzene (BHT 0.5 mg / mL added)
Elution flow rate: 1 mL / min Measurement time: Approx. 1 hour

[GPC device]
As a GPC apparatus equipped with a differential refractometer (RI), HLC-8121 GPC / HT manufactured by Tosoh Corporation was used. Moreover, PD2040 of Precision Detectors was connected to the said GPC apparatus as a light-scattering detector (LS). The scattering angle used for light scattering detection was 90 °. In addition, a Viscotek H502 was connected to the GPC apparatus as a viscosity detector (VISC). LS and VISC were installed in the column oven of the GPC apparatus and connected in the order of LS, RI, and VISC. For calibration of LS and VISC and correction of delay capacity between detectors, PolyTDS-PS-N (weight average molecular weight Mw 104,349, polydispersity 1.04), a polystyrene standard material of Malvern, was 1 mg / mL. The solution concentration was used. For the mobile phase and the solvent, orthodichlorobenzene added with dibutylhydroxytoluene at a concentration of 0.5 mg / mL as a stabilizer was used. The sample was dissolved at 145 ° C. for 2 hours. The flow rate was 1 mL / min. As the column, three Tosoh Corporation GMHHR-H (S) HT were connected and used. The temperature of the column, sample injection section and each detector was 155 ° C. The sample solution concentration was 2 mg / mL. The injection amount of the sample solution (sample loop volume) was 0.3 mL. The refractive index increment (dn / dc) of NIST1475a and the sample in orthodichlorobenzene was −0.078 mL / g. The dn / dc of the polystyrene standard material was 0.079 mL / g. In obtaining the absolute molecular weight and intrinsic viscosity ([η]) from the data of each detector, Malvern's data processing software OmniSEC (version 4.7) is used, and the document “Size Exclusion Chromatography, Springer (1999)” is referred. The calculation was performed. The refractive index increment is the rate of change of the refractive index with respect to the density change.

Α ₁ and α ₀ of formula (I) were obtained by the following method, and both were substituted into formula (I) to obtain A.
A = α ₁ / α ₀ (I)
α ₁ is a plot of the measured data with the logarithm of the absolute molecular weight of the polymer as the horizontal axis and the logarithm of the intrinsic viscosity of the polymer as the vertical axis. The horizontal axis represents the logarithm of the absolute molecular weight and the logarithm of the intrinsic viscosity. In the range from the logarithm of the weight average molecular weight to the logarithm of the z average molecular weight to the logarithm of the z average molecular weight, the least square method is approximated by the formula (II), and the value of the slope of the straight line representing the formula (II) is α _1. It is the value obtained by the method of including.
log [η ₁ ] = α ₁ logM ₁ + logK ₁ (I−I)
(In formula (II), [η ₁ ] represents the intrinsic viscosity (unit: dl / g) of the polymer, M ₁ represents the absolute molecular weight of the polymer, and K ₁ is a constant.)
The measured data is plotted with the logarithm of the absolute molecular weight of the polyethylene standard material 1475a as the horizontal axis and the logarithm of the intrinsic viscosity of the polyethylene standard material 1475a as the vertical axis, and the horizontal axis represents the logarithm of the absolute molecular weight and the logarithm of the intrinsic viscosity. In the range from the logarithm of the weight average molecular weight of the substance 1475a to the logarithm of the z average molecular weight, the least square method is approximated by the formula (I-II), and the value of the slope of the straight line representing the formula (I-II) is α _0. Is a value obtained by a method including
log [η ₀ ] = α ₀ logM ₀ + log K ₀ (I-II)
(In the formula (I-II), [η ₀ ] represents the intrinsic viscosity (unit: dl / g) of the polyethylene standard material 1475a, M ₀ represents the absolute molecular weight of the polyethylene standard material 1475a, and K ₀ is a constant. .)

[IV] Physical property evaluation method of resin composition before adding blowing agent (1) Melt flow rate (MFR, unit: g / 10 min)
The melt flow rate of the resin composition was measured according to the method defined in JIS K7210.
The measurement temperature was 230 ° C. and the load was 2.16 kg.

[V] Method for evaluating physical properties of foam (1) Foam moldability For the foams produced under the conditions described in Examples and Comparative Examples, the expansion ratio was measured. The expansion ratio can be determined by (density of resin composition before foaming) / (density of foam).

[VII] Raw Material <Precursor Polymer Having Structural Unit (A) and Structural Unit (C)>
A-1: Ethylene-methyl acrylate copolymer Ethylene-methyl acrylate copolymer A-1 was produced as follows.
In an autoclave reactor, ethylene and methyl acrylate are copolymerized by copolymerizing ethylene and methyl acrylate using tert-butyl peroxypivalate as a radical polymerization initiator at a reaction temperature of 195 ° C. and a reaction pressure of 160 MPa. A-1 was obtained. The composition and MFR of the obtained copolymer A-1 were as follows. Number of structural units derived from ethylene: 85.3% (65.4% by weight), number of structural units derived from methyl acrylate: 14.7% (34.6% by weight), MFR (at 190 ° C., 21 N Measurement): 41 g / 10 min

<Compound having an alkyl group having 14 to 30 carbon atoms>
B-1: GINOL-16 (n-hexadecyl alcohol) [manufactured by GODREJ]

<Catalyst>
C-1: Tetra orthotitanate (iso-propyl) [Nippon Soda Co., Ltd.]

<Polystyrene (polystyrene (2))>
D-1: Toyostyrene GP HRM48N (styrene homopolymer) [manufactured by Toyo Styrene Co., Ltd.]
<Copolymer (Copolymer (3))>
E-1: Tuftec H1221 (hydrogenated styrene-butadiene-styrene block copolymer) [manufactured by Asahi Kasei Chemicals Corporation]

<Organic peroxide (crosslinking agent)>
F-1: Kayahexa AD-40C (a mixture containing 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, calcium carbonate and amorphous silicon dioxide) (1 minute half-life temperature: 180 ° C. ) [Kayaku Akzo Corporation]

<Crosslinking aid>
G-1: High Cloth MS50 (mixture of trimethylolpropane trimethacrylate and amorphous silicon dioxide) [manufactured by Seiko Chemical Co., Ltd.]

<Foaming agent>
H-1: Cell microphone MB3074 (decomposition temperature: 170-210 ° C.) [manufactured by Sankyo Kasei Co., Ltd.]

<Antioxidant>
I-1: IRGANOX 1010 (pentaerythritol = tetrakis [3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate]) [manufactured by BASF]

<Processing heat stabilizer>
J-1: IRGAFOS 168 (Tris (2,4-di-tert-butylphenyl) phosphite) [manufactured by BASF]

<Extruder>
○ Twin screw extruder (1)
・ Barrel diameter D = 44mm
・ Screw effective length L / barrel diameter D = 42
○ Twin screw extruder (2)
・ Barrel diameter D = 15mm
・ Screw effective length L / barrel diameter D = 45
○ Single screw extruder (1)
・ Barrel diameter D = 20mm
・ Screw effective length L / barrel diameter D = 27
・ Die: Coat hanger die with 100mm width lip adjustment bolt ・ Rip gap: Set to 2mm on average

Reference example 1
(1) Production of a polymer (ethylene-n-hexadecyl acrylate-methyl acrylate copolymer) comprising the structural unit (A), the structural unit (B), and the structural unit (C) Inside of a reactor equipped with a stirrer Was replaced with nitrogen, A-1: 100 parts by weight, B-1: 84.4 parts by weight, C-1: 0.2 parts by weight were added, and the jacket temperature was set at 140 ° C. for 12 hours under a reduced pressure of 1 kPa. The mixture was heated and stirred to obtain a polymer (cf1) (ethylene-n-hexadecyl acrylate-methyl acrylate copolymer). Table 1 shows the physical property values and evaluation results of the polymer (cf1).

Reference example 2
(1) Preparation of crosslinked resin composition (resin composition containing crosslinked ethylene-n-hexadecyl acrylate-methyl acrylate copolymer and polystyrene homopolymer) Obtained in Reference Example 1 (1) Polymer (cf1): 80 parts by weight, D-1: 20 parts by weight, F-1: 1.5 parts by weight, G-1: 1.0 parts by weight, I-1: 0.1 Part by weight and J-1: 0.1 part by weight using a twin screw extruder (1), screw rotation speed 400 rpm, discharge rate 30 kg / hr, barrel first half temperature 200 ° C., barrel second half temperature 220 ° C. The resin composition (cf2) was extruded by extrusion at a die temperature of 200 ° C. Table 2 shows the MFR and density of the resin composition (cf2).

Example 1
(1) Preparation of a crosslinked resin composition (a resin comprising a crosslinked ethylene-n-hexadecyl acrylate-methyl acrylate copolymer, a polystyrene homopolymer, and a hydrogenated styrene-butadiene-styrene block copolymer) Composition)
Resin composition (cf2) obtained in Reference Example 2 (1): 50 parts by weight, D-1: 45 parts by weight, and E-1: 5 parts by weight using a twin screw extruder (2) Extrusion was performed at a screw rotation speed of 500 rpm, a discharge rate of 1.5 kg / hr, a barrel first half temperature of 180 ° C., a barrel second half temperature of 200 ° C., and a die temperature of 200 ° C. to produce a crosslinked resin composition (ex1). Table 3 shows the density of the resin composition (ex1).
(2) Production of Foam Resin composition (ex1) obtained in Example 1 (1): 100 parts by weight and H-1: 2 parts by weight using a single screw extruder (1), screw Extrusion was performed at a rotational speed of 55 to 80 rpm, a discharge rate of 2 kg / hr, a barrel first half temperature of 60 to 180 ° C., a barrel second half temperature of 175 to 190 ° C., and a die temperature of 148 to 168 ° C. to obtain a foam. The results are shown in Table 3. The foaming ratio of the foam was 1.21 times, and the foam moldability was good.

Example 2
(1) Preparation of a crosslinked resin composition (a resin comprising a crosslinked ethylene-n-hexadecyl acrylate-methyl acrylate copolymer, a polystyrene homopolymer, and a hydrogenated styrene-butadiene-styrene block copolymer) Composition)
D-1: Crosslinked resin composition (ex2) in the same manner as in Example 1 (1) except that 45 parts by weight is changed to 40 parts by weight and E-1: 5 parts by weight is changed to 10 parts by weight. Was made. Table 3 shows the density of the resin composition (ex2).
(2) Production of Foam Resin Composition (ex1) Obtained in Example 1 (1): 100 parts by weight Resin composition (ex2) obtained in Example 2 (1): 100 parts by weight A foam was obtained in the same manner as in Example 1 (2) except that. The results are shown in Table 3. The foaming ratio of the foam was 1.40 times, and the foam moldability was good.

Example 3
(1) Preparation of a crosslinked resin composition (a resin comprising a crosslinked ethylene-n-hexadecyl acrylate-methyl acrylate copolymer, a polystyrene homopolymer, and a hydrogenated styrene-butadiene-styrene block copolymer) Composition)
D-1: Crosslinked resin composition (ex3) in the same manner as in Example 1 (1) except that 45 parts by weight is changed to 35 parts by weight and E-1: 5 parts by weight is changed to 15 parts by weight. Was made.
(2) Production of foam: Resin composition (ex1) obtained in Example 1 (1): 100 parts by weight Resin composition (ex3) obtained in Example 3 (1): 100 parts by weight A foam was obtained in the same manner as in Example 1 (2) except that. The results are shown in Table 3. The foaming ratio of the foam was 1.58 times, and the foam moldability was good.

Claims (10)

Polymer (1) having a melting enthalpy of 30 J / g or more observed in a temperature range of 10 ° C. or more and less than 60 ° C. by differential scanning calorimetry 10% to 90% by weight,
Polystyrene (2) 10 wt% or more and 90 wt% or less,
And a copolymer (3) having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound (3) a resin composition containing 0.1% by weight to 50% by weight (however, the polymer (1), the total amount of polystyrene (2) and the copolymer (3) is 100% by weight). The resin composition according to claim 1, wherein the polymer (1) is a polymer having a structural unit (B) represented by the following formula (1).

(In the formula (1),
R represents a hydrogen atom or a methyl group,
L ¹ represents a single bond, —CO—O—, —O—CO—, or —O—,
L ² represents a single _{bond, -CH 2 -, - CH 2} -CH 2 -, - CH 2 -CH 2 -CH 2 -, - CH 2 -CH (OH) -CH 2 -, or _-CH 2 -CH (CH ₂ OH) —
L ³ is a single bond, —CO—O—, —O—CO—, —O—, —CO—NH—, —NH—CO—, —CO—NH—CO—, —NH—CO—NH—. , -NH-, or -N (CH ₃ )-
L ⁶ represents an alkyl group having 14 to 30 carbon atoms,
Each of the horizontal chemical formulas in the description of the chemical structures of L ¹ , L ² , and L ³ corresponds to the upper side of the formula (1) on the left side and the lower side of the formula (1) on the right side. ) The polymer (1) has a structural unit (A) derived from ethylene and a structural unit (B) represented by the following formula (1), and further a structural unit represented by the following formula (2) and And at least one structural unit (C) selected from the group consisting of structural units represented by formula (3),
When the total number of the structural unit (A), the structural unit (B), and the structural unit (C) is 100%, the number of the structural units (A) is 70% or more and 99% or less, The total number of the structural unit (B) and the structural unit (C) is 1% or more and 30% or less,
When the total number of the structural unit (B) and the structural unit (C) is 100%, the number of the structural units (B) is 1% or more and 100% or less, and the number of the structural units (C). The resin composition according to claim 1 or 2, which is a polymer having a content of 0% or more and 99% or less.

(In the formula (1),
R represents a hydrogen atom or a methyl group,
L ¹ represents a single bond, —CO—O—, —O—CO—, or —O—,
L ² represents a single _{bond, -CH 2 -, - CH 2} -CH 2 -, - CH 2 -CH 2 -CH 2 -, - CH 2 -CH (OH) -CH 2 -, or _-CH 2 -CH (CH ₂ OH) —
L ³ is a single bond, —CO—O—, —O—CO—, —O—, —CO—NH—, —NH—CO—, —CO—NH—CO—, —NH—CO—NH—. , -NH-, or -N (CH ₃ )-
L ⁶ represents an alkyl group having 14 to 30 carbon atoms,
Each of the horizontal chemical formulas in the description of the chemical structures of L ¹ , L ² , and L ³ corresponds to the upper side of the formula (1) on the left side and the lower side of the formula (1) on the right side. )

(In the formula (2),
R represents a hydrogen atom or a methyl group,
L ¹ represents a single bond, —CO—O—, —O—CO—, or —O—,
L ⁴ represents an alkylene group having 1 to 8 carbon atoms,
L ⁵ represents a hydrogen atom, an epoxy group, —CH (OH) —CH ₂ OH, a carboxy group, a hydroxy group, an amino group, or an alkylamino group having 1 to 4 carbon atoms,
Each of the horizontal chemical formulas in the description of the chemical structure of L ¹ corresponds to the upper side of the formula (2) on the left side and the lower side of the formula (2) on the right side. )

  The polymer (1) includes the structural unit (A) and the structural unit (B), and may further include the structural unit (C), and is included in the polymer. The polymer in which the total number of the structural unit (A), the structural unit (B), and the structural unit (C) is 90% or more when the total number of all the structural units is 100%. 3. The resin composition according to 3. The resin composition according to any one of claims 1 to 4, wherein a ratio A defined by the following formula (I) of the polymer (1) is 0.95 or less.
A = α ₁ / α ₀ (I)
[In the formula (I), α ₁ is
Measure the absolute molecular weight and intrinsic viscosity of the polymer by gel permeation chromatography using a device with a light scattering detector and a viscosity detector,
The measured data is plotted with the logarithm of the absolute molecular weight as the horizontal axis and the logarithm of the intrinsic viscosity as the vertical axis. This is a value obtained by a method including approximation by the least squares method with the formula (II) in a range equal to or lower than the logarithm of the molecular weight and setting the value of the slope of the straight line representing the formula (II) as α ₁ .
log [η ₁ ] = α ₁ logM ₁ + logK ₁ (I−I)
(In formula (II), [η ₁ ] represents the intrinsic viscosity (unit: dl / g) of the polymer, M ₁ represents the absolute molecular weight of the polymer, and K ₁ is a constant.)
In the formula (I), α ₀ is
The absolute molecular weight and intrinsic viscosity of polyethylene standard substance 1475a (manufactured by National Institute of Standards and Technology) are measured by gel permeation chromatography using a device equipped with a light scattering detector and a viscosity detector.
The measured data is plotted with the logarithm of absolute molecular weight as the horizontal axis and the logarithm of intrinsic viscosity as the vertical axis. in logarithmic the range of z-average molecular weight approximating the minimum square method by the formula (I-II), a value obtained by a process comprising the value of the slope of the straight line representing the formula (I-II) and alpha ₀ is there.
log [η ₀ ] = α ₀ logM ₀ + log K ₀ (I-II)
(In the formula (I-II), [η ₀ ] represents the intrinsic viscosity (unit: dl / g) of the polyethylene standard material 1475a, M ₀ represents the absolute molecular weight of the polyethylene standard material 1475a, and K ₀ is a constant. .)
In the measurement of the absolute molecular weight and intrinsic viscosity of the polymer and polyethylene standard substance 1475a by gel permeation chromatography, the mobile phase is orthodichlorobenzene and the measurement temperature is 155 ° C. ]   The resin composition according to any one of claims 1 to 5, wherein the polymer (1) is a crosslinked polymer.   The resin composition according to any one of claims 1 to 6, wherein the gel fraction is 20% by weight or more (provided that the weight of the resin composition is 100% by weight).   The resin composition according to any one of claims 1 to 7, wherein the copolymer (3) is a hydrogenated product of an aromatic vinyl compound-conjugated diene compound-aromatic vinyl compound copolymer.   The molded object containing the resin composition as described in any one of Claims 1-8.   The foam containing the resin composition as described in any one of Claims 1-8.