JP2017227329A - Laminate and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate excellent in adhesiveness to wallpaper, and a method of manufacturing the laminate.SOLUTION: A laminate includes: a heat storage layer 1 containing a polymer 1 whose enthalpy of fusion observed within a temperature range of 10°C or more and less than 60°C with differential scanning calorimetry is 30 J/g or more; an intermediate layer 2 comprising a polymer 2 (where, excepting the polymer 1) which is adjacent to the heat storage layer 1, and whose fusion peak temperature or glass transition temperature observed with the differential scanning calorimetry is 50°C or more and 180°C or less; and a base material layer 3 adjacent to the intermediate layer 2 and comprising paper.SELECTED DRAWING: None

Description

  The present invention relates to a laminate and a method for producing the same.

  It is known that a heat storage material is used as a building material such as a wall material. Patent Document 1 describes that a crystalline higher α-olefin polymer obtained by copolymerizing a higher α-olefin having 10 or more carbon atoms and another olefin is used as a heat storage material.

Japanese Patent Laying-Open No. 2005-75908 (published on March 24, 2005)

  When the heat storage material is used as a part of the wall material, a construction method in which a sheet made of the heat storage material is attached to a gypsum board and adhered to wallpaper is considered. However, the sheet made of the polymer is not sufficiently adhesive to wallpaper.

（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）とを有し、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）に記載の積層体。
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積層体。
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積層体。
７） 前記重合体（１）のゲル分率が２０重量％以上である（ただし、重合体（１）の重量を１００重量％とする）１）〜６）のいずれかに記載の積層体。
８） 前記重合体（２）が、エチレンに由来する構成単位を含む重合体である１）〜７）のいずれかに記載の積層体。
９） 前記蓄熱層（１）を有する成形体と、前記中間層（２）および前記基材層（３）を有する成形体の中間層（２）と
を加熱接着する工程を含む１）〜８）のいずれかに記載の積層体の製造方法。 In order to solve the above problems, one of the following is provided.
1) A heat storage layer (1) containing a 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, the heat storage layer (1) An intermediate composed of a polymer (2) which is a polymer (excluding polymer (1)) which is adjacent and has a melting peak temperature or glass transition temperature of 50 ° C. or higher and 180 ° C. or lower as observed by differential scanning calorimetry. A laminate having a layer (2) and a base material layer (3) made of paper adjacent to the intermediate layer (2).
2) The heat storage layer (1) contains the polymer (1) and the polymer (2), and the total amount of the polymer (1) and the polymer (2) is 100% by weight. The content of the polymer (1) is 30 wt% or more and 99 wt% or less, and the content of the polymer (2) is 1 wt% or more and 70 wt% or less. Laminated body.
3) The polymer (1) has a structural unit (A) derived from ethylene and a structural unit (B) represented by the following formula (1), and a structural unit represented by the following formula (2) and It may have at least one structural unit (C) selected from the group consisting of structural units represented by the following formula (3), and 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%. 30% or less, 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% or more and 100% or less, The laminate according to 1) or 2), which is a polymer in which the number of structural units (C) is from 0% to 99% .

(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- and represents, ^{L 2} is 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)} - represents, ^{L 3} represents 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, and each of the horizontal chemical formulas in the description of the chemical structures of L ¹ , L ² , and L ³ is the left side of the formula (1), The right side corresponds to the lower side of equation (1). )

(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, Represents 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, and 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 the expression (2), and the right side corresponds to the lower side of the expression (2). )

4) The polymer (1) includes the structural unit (A) and the structural unit (B), and may further include the structural unit (C), and the polymer 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 in The laminated body as described in 3).
5) The laminate 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 the logarithm of the absolute molecular weight obtained by measuring the absolute molecular weight and the intrinsic viscosity of the polymer by gel permeation chromatography using an apparatus equipped with a light scattering detector and a viscosity detector. Is plotted with the logarithm of the intrinsic viscosity and the logarithm of the intrinsic viscosity as the vertical axis, and the logarithm of the absolute molecular weight and the logarithm of the intrinsic viscosity are plotted, and the horizontal axis is the logarithm of the weight average molecular weight of the polymer and the logarithm of the z average molecular weight. Is a value obtained by a method including the approximation of the least squares method using the formula (II) in the range of α and 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 formula (I), α ₀ is the absolute molecular weight of polyethylene standard substance 1475a (manufactured by National Institute of Standards and Technology) by gel permeation chromatography using a device equipped with a light scattering detector and a viscosity detector. Intrinsic viscosity was measured, the logarithm of absolute molecular weight was plotted on the horizontal axis, the logarithm of intrinsic viscosity was plotted on the vertical axis, and the measured data was plotted. The logarithm of absolute molecular weight and the logarithm of intrinsic viscosity were plotted on the horizontal axis of the polyethylene standard material 1475a. A method including the least square method approximation by the formula (I-II) in the range of the logarithm of the weight average molecular weight to the logarithm of the z average molecular weight, and the value of the slope of the straight line representing the formula (I-II) being α ₀ Is the value obtained by
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 laminate according to any one of 1) to 5), wherein the polymer (1) is a crosslinked polymer.
7) The laminate according to any one of 1) to 6), wherein the gel fraction of the polymer (1) is 20% by weight or more (provided that the weight of the polymer (1) is 100% by weight).
8) The laminate according to any one of 1) to 7), wherein the polymer (2) is a polymer containing a structural unit derived from ethylene.
9) 1) -8 including the process which heat-bonds the molded object which has the said thermal storage layer (1), and the intermediate | middle layer (2) of the molded object which has the said intermediate | middle layer (2) and the said base material layer (3). The manufacturing method of the laminated body in any one of.

  The present invention provides a laminate having a heat storage layer, which is excellent in adhesiveness to wallpaper, and a method for producing the laminate.

[1. (Laminated body)
The laminate of the present invention comprises a heat storage layer (1) comprising a 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, the heat storage layer A polymer (2 excluding polymer (1)) adjacent to (1) and having a melting peak temperature or glass transition temperature of 50 ° C. or higher and 180 ° C. or lower as observed by differential scanning calorimetry And an intermediate layer (2) made of paper and adjacent to the intermediate layer (2). In the following, the melting enthalpy may be expressed as ΔH. First, each material of a laminated body is demonstrated below.

<Polymer (1)>
The polymer (1) is a polymer having a melting enthalpy (ΔH) 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. ΔH observed within a temperature range of 10 ° C. or more and less than 60 ° C. is preferably 50 J / g or more, and more preferably 70 J / g or more. The ΔH is usually 200 J / g or less.

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 heat storage layer (1) 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 the formula (1) is an alkyl group having 14 to 30 carbon atoms so that the moldability of the polymer (1) that is a constituent material of the heat storage layer (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.

式（１）におけるＲ、Ｌ^１、Ｌ^２及びＬ^３の組み合わせとして、以下のものも好ましい。
Ｒが水素原子、Ｌ^１、Ｌ^２及びＬ^３が単結合であり、Ｌ^６が炭素原子数１４以上３０以下のアルキル基であるか、
Ｒが水素原子またはメチル基であり、Ｌ^１が−ＣＯ−Ｏ−であり、Ｌ^２およびＬ^３が単結合であり、Ｌ^６が炭素原子数１４以上３０以下のアルキル基である。 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) is derived from ethylene so that the shape retention of the laminate at the melting peak temperature of the polymer (1) and the molding processability of the polymer (1) are good. A polymer having a unit (A) is preferred. 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),
A polymer (1) having the structural unit (B) and the structural unit (C), and a 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. 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 an alkyl group having 14 to 30 carbon atoms. And a polymer composed of the structural unit (B) represented by the formula (1).

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 formula (1) as the following 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 positions (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 such that when the total number of the structural units (A), the structural units (B), and the structural units (C) is 100%, It is preferably 70% or more and 99% or less, more preferably 80% or more and 97.5% or less, and still more preferably so that the shape retention of the heat storage layer (1) including the coalescence (1) is good. It is 85% or more and 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, more preferably 2.5% or more and 20% so that the shape retention of the heat storage layer (1) containing the polymer (1) is good. % Or less, more preferably 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, more preferably 80% or more and 100% or less so that the heat storage performance of the heat storage layer (1) 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%. Preferably, it is 0% or more and 40% or less, more preferably 0% or more and 20% or less so that the heat storage performance of the heat storage layer (1) 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 formula (2) and the structural unit represented by the 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)
The structural unit (C) contained in the precursor polymer (1) and the compound (α) react to form the structural unit (B) in the polymer (1). 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 A method of reacting at least one kind of compound, a method of polymerizing a monomer that is a raw material of the structural unit (B), and a method of copolymerizing ethylene and a monomer that is a raw material of the structural unit (B). It is done. 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 as a raw material for the structural unit (B) or a method of copolymerizing ethylene and a monomer as a raw material for the structural unit (B). The alkyl group of the compound (α) is preferably a linear alkyl group. A polymerization initiator such as an azo compound may be used in the method for polymerizing the monomer. 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, 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) The product r1r2 of the reactivity ratio when the reactivity ratio of the monomer to be formed is set to r2 is preferably 0. 0 so that the shape retention of the heat storage layer (1) containing the precursor polymer (1) is good. 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 copolymerization of ethylene and the monomer that forms the structural unit (C).
It is an index showing whether the polymer having the terminal structural unit (A) is more easily reacted with ethylene or the monomer forming the structural unit (C). 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). This is a value defined by r2 = k22 / k21 where k21 is the reaction rate and k22 is the reaction rate at which the monomer forming the structural unit (C) is bonded 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 from 0.1 g / 10 min to 500 g / 10 min.

  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 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.

  A catalyst may be added to promote the reaction when the precursor polymer (1) is reacted with at least one kind of the compound (α). 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 parts 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) is preferably derived from ethylene so that the shape retention of the laminate above the melting peak temperature of the polymer (1) and the moldability of the polymer (1) are good. The structural unit (A). More preferably, the structural unit (A) derived from ethylene forms a branched structure in the polymer, more preferably so that the blow moldability and foam moldability of the polymer (1) are good. 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.)]

  In obtaining the absolute molecular weight from the data obtained by the light scattering detector and obtaining the intrinsic viscosity ([η]) by the viscosity detector, the data processing software OmniSEC (version 4.7) of Malvern is used, and the document “Size” is used. 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 : activation energy of flow (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 gel fraction of a polymer to be described later of less than 20% by weight.
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.
Examples of the method of crosslinking the polymer (1) include a method of irradiating with ionizing radiation and a method of crosslinking using an organic peroxide.

  When crosslinking is performed by irradiating the polymer (1) with ionizing radiation, the polymer (α) molded in 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 body to be irradiated with ionizing radiation may be a molded body containing only the polymer (1) as a resin component, and a molded body containing the polymer (1) and a polymer different from the polymer (1). But you can. In the latter case, a polymer different from the polymer (1) includes a polymer (2) described later. When the molded body contains the polymer (1) and the polymer (2), when the total amount of the polymer (1) and the polymer (2) is 100% by weight, the polymer (1) The content is preferably 30% by weight or more and 99% 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 (1) is in the form of a sheet, 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 polymer (1) that is crosslinked by irradiation with ionizing radiation, the polymer (1) that is irradiated with ionizing radiation contains a crosslinking aid so that a crosslinked polymer having a higher degree of crosslinking ( 1) can be obtained. The crosslinking aid is for increasing the degree of crosslinking of the polymer (1) 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.

  The addition amount of the crosslinking aid is 0 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. 0.01 to 4.0 parts by weight is preferable, and 0.05 to 2.0 parts by weight is more preferable.

Examples of the method of crosslinking using an organic peroxide include 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 only the polymer (1) as a resin component, and the polymer (1) and a polymer different from the polymer (1) May be included.
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 the polymer (2) described later, When the total amount of the polymer (1) and the polymer (2) is 100% by weight, the content of the polymer (1) is preferably 30% by weight or more and 99% 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 a known additive as required. 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 the polymer (1) 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. That's it. 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). Netting and xylene encapsulating a polymer (Kanto Chemical Co., Ltd., deer special grade or equivalent: 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

  Examples of the laminate include sheet shapes, plate shapes, and film shapes, and the heat storage layer (1), the intermediate layer (2), and the base material layer (3) are laminated layers having the same shape. It may have a structure. In particular, when used as part of a building material such as a wall material, the heat storage layer (1), the intermediate layer (2), and the base material layer (3) are each preferably a sheet-like laminate.

<Heat storage layer (1)>
The laminate of the present invention comprises a heat storage layer (1) comprising a polymer (1) having a melting enthalpy (ΔH) 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. Have

  In one embodiment, the heat storage layer (1) includes the polymer (1) and a polymer having a melting peak temperature or a glass transition temperature of 50 ° C. or higher and 180 ° C. or lower observed by differential scanning calorimetry (however, the polymer (Excluding (1)), and when the total amount of the polymer (1) and the polymer (2) is 100% by weight, the heat storage layer (1 ) Contained in the polymer (1) is 30 wt% or more and 99 wt% or less, and the content of the polymer (2) is 1 wt% or more and 70 wt% or less. The contents of the polymer (1) and the polymer (2) contained in the heat storage layer (1) are 100% by weight of the total amount of the polymer (1) and the polymer (2), respectively. In this case, the content of the polymer (1) is preferably 40% by weight or more and 95% by weight or less, and the content of the polymer (2) is preferably 5% by weight or more and 60% by weight or less. More preferably, the content of 1) is 50% by weight or more and 90% by weight or less, the content of the polymer (2) is 10% by weight or more and 50% by weight or less, and the content of the polymer (1) is More preferably, they are 60 weight% or more and 85 weight% or less, and content of a polymer (2) is 15 weight% or more and 40 weight% or less. The polymer (2) is described in detail in <Intermediate layer (2)>. When the polymer (2) is used for the heat storage layer (1), the polymer (2) used for the intermediate layer (2) may be the same as that used for the intermediate layer (1). May be different.

  Hereinafter, the resin composition constituting the heat storage layer (1) containing the polymer (1) and the polymer (2) may be hereinafter referred to as a resin composition (A).

  The polymer (1) may be composed of two or more kinds of polymers, and the polymer (2) may be composed of two or more kinds of polymers.

The melting peak temperature or glass transition temperature observed by differential scanning calorimetry (DSC) of the polymer (2) is in the range of 50 ° C. or higher and 180 ° C. or lower. The melting peak temperature of the polymer (2) is the temperature at the apex of the melting peak obtained by analyzing the melting curve measured by the following differential scanning calorimetry by a method according to JIS K7121-1987. This is the temperature at which the amount of heat is maximized.
The glass transition temperature of the polymer (2) is an intermediate glass transition temperature obtained by analyzing a melting curve measured by the following differential scanning calorimetry by a method according to JIS K7121-1987.
[Differential scanning calorimetry]
By means of a differential scanning calorimeter, an aluminum pan encapsulating about 5 mg of sample in a nitrogen atmosphere was (1) held at 200 ° C. for 5 minutes, then (2) 200 ° C. to −50 at a rate of 5 ° C./min The temperature is then lowered to 3 ° C., then (3) held at −50 ° C. for 5 minutes, and (4) the temperature is raised from −50 ° C. to 200 ° 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 thickness of the heat storage layer (1) is usually from 10 μm to 200 mm, preferably from 100 μm to 10 mm, more preferably from 500 μm to 5 mm, and still more preferably from 1 mm to 3 mm.

  In one embodiment, the heat storage layer (1) is a non-foamed layer made of a non-foamed material.

<Heat storage layer (1) which is a foam layer>
The heat storage layer (1) is a foam layer made of a foam obtained by foaming a resin composition (hereinafter sometimes referred to as a resin composition (B)) containing the polymer (1) and a foaming agent. There may be.

  Examples of the foaming agent include physical foaming agents and pyrolytic foaming agents. A plurality of foaming agents may be used in combination. The resin composition (B) may contain a polymer different from the polymer (1). In the case where the resin composition (B) contains a polymer different from the polymer (1), the polymer (2) may be mentioned as the polymer. When the resin composition (B) contains the polymer (1) and the polymer (2), the total amount of the polymer (1) and the polymer (2) is 100% by weight. The content of the polymer (1) is preferably 30% by weight or more and 99% by weight or less, and the content of the polymer (2) is more preferably 1% by weight or more and 70% by weight or less.

  Physical foaming agents include air, oxygen, nitrogen, carbon dioxide, ethane, propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, cyclohexane, heptane, ethylene, propylene, water, petroleum ether, Examples include 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

  Examples of the thermally decomposable foaming agent include inorganic foaming agents such as sodium carbonate, and organic systems such as azodicarbonamide, N, N-dinitropentamethylenetetramine, p, p′-oxybisbenzenesulfonylhydrazide, and hydrazodicarbonamide. Among them, azodicarbonamide, sodium hydrogen carbonate, p, p′-oxybisbenzenesulfonyl hydrazide are preferable from the viewpoint of economy and safety, and the molding temperature range is wide and the bubbles are fine. Since a foam is 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 resin composition containing at least one of polymer (1), polymer (2), or polymer (1) and (2) 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 preferably obtained by melt-kneading the polymer (1), a foaming agent, and other components blended as necessary. As a method of melt-kneading, for example, after mixing the polymer (1) and a foaming agent with a mixing device such as a tumbler blender or a Henschel mixer, the method is further melt-kneaded with a single-screw 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 the production of the foam containing the polymer (1), and extrusion foam molding, injection foam molding, pressure foam molding and the like are preferably used.

  In the case where 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 (1) 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 irradiation with radiation or melt-kneading the crosslinked polymer (1) and the foaming agent; A method of heating the resin composition (α) to produce a foam (hereinafter referred to as a method (A)), and in a sealed mold, the polymer (1), A resin composition containing a foaming agent and an organic peroxide, or a polymer (1) that is cross-linked by pressurizing while heating a resin composition containing a cross-linked polymer (1) and a foaming agent. And a step of producing a resin composition (β) containing a foam from the resin composition (β) by opening a mold Method comprising the step of producing a (hereinafter, referred to as method (B)) and the like.

<Production Method of Foam: Production Method by Method (A)>
The method (A) will be specifically described below.
The method (A) includes a step of producing a resin composition (α) containing a crosslinked polymer (1) and a foaming agent (hereinafter referred to as a resin composition (α) production step), and the resin composition. Heating the product (α) to produce a foam (hereinafter referred to as a foam production process). Hereinafter, each step will be described.

[Production process of resin composition (α)]
The resin composition containing the polymer (1) and the foaming agent in the resin composition (α) production process for producing the resin composition (α) containing the crosslinked polymer (1) and the foaming agent is ionizable. In the case of producing by irradiating with radiation, the ionizing radiation used for irradiating the resin composition containing the polymer (1) and the foaming agent is ionizable used for the production of the crosslinked polymer (1). Irradiation rays are mentioned. 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 (1) 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.

[Foam manufacturing process]
In the foam production process for 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. A method capable of continuously heating and foaming the resin composition (α) such as a mold hot air foaming 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 when the foaming agent is a thermal decomposition type foaming agent, the temperature is preferably 5 to 50 ° C. higher than the decomposition temperature of the thermal decomposition type foaming agent, more preferably thermal decomposition. The temperature is 10 to 40 ° C. higher than the decomposition temperature of the mold blowing agent, and more preferably 15 to 30 ° C. higher than the decomposition temperature of the thermal decomposition blowing 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.

<Method for producing foam: production method by method (B)>
Next, the method (B) will be specifically described below.

  In the method (B), the polymer (1), a foaming agent, and a resin composition containing an organic peroxide, or a crosslinked polymer (1) and a foam are sealed in a sealed mold. A step of producing a resin composition (β) containing a crosslinked polymer (1) by pressurizing the containing resin composition while heating (hereinafter referred to as a resin composition (β) production step), and molding And a step of manufacturing a foam from the resin composition (β) by opening a mold (hereinafter referred to as a foam manufacturing step). Hereinafter, each step will be described.

[Production process of resin composition (β)]
In the resin composition (β) production step, the polymer (1), the foaming agent, and the resin composition containing the organic peroxide are heated and pressurized in a mold while being heated to form a crosslinked polymer ( In the case of producing a resin composition (β) containing 1), examples of the organic peroxide include organic peroxides that can be used in the production of the crosslinked polymer of the present invention.

  The resin composition to be pressed while heating in a mold is a resin comprising the polymer (1), a foaming agent, an organic peroxide, or a crosslinked polymer (1) and a foam in advance. The composition is preferably a resin composition obtained by melt-kneading the composition at a temperature lower than the decomposition temperature of the foaming agent and lower than the one minute half-life temperature of the organic peroxide.

  In the case of the resin composition containing the polymer (1), the foaming agent, and the organic peroxide in the mold, the temperature for heating the resin composition is not less than the 1 minute half-life temperature of the organic peroxide. Thus, a temperature equal to or higher than the decomposition temperature of the foaming agent is preferable.

[Foam manufacturing process]
In the foam manufacturing process of opening the mold and manufacturing the foam from the resin composition (β), it is preferable to open the mold after cooling the mold to 40 ° C. or higher and 100 ° C. or lower. 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.

  Further, in order to increase the foaming ratio and strength of the foam containing the crosslinked polymer (1) of the present invention, the resin composition containing the polymer (1) and the foaming agent further comprises a crosslinking aid. It is preferable to include. Examples of the crosslinking aid include the crosslinking aid used in the production of the crosslinked polymer (1) of the present invention. The amount of the crosslinking aid contained in the resin composition containing the polymer (1), 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.

<Intermediate layer (2)>
The laminate of the present invention is a polymer having a melting peak temperature or glass transition temperature observed by differential scanning calorimetry of 50 ° C. or higher and 180 ° C. or lower (however, a temperature range of 10 ° C. or higher and lower than 60 ° C. by differential scanning calorimetry. It has an intermediate layer (2) composed of a polymer (2) which is a polymer having a melting enthalpy (ΔH) of 30 J / g or more). The intermediate layer (2) is adjacent to the heat storage layer (1). Note that “adjacent” means a state in which one layer and the other layer are in close contact with each other in the laminate.

  The intermediate layer (2) may be adjacent to any one surface of the storage layer (1), or may be adjacent to both surfaces of the storage layer (1).

  The melting peak temperature or glass transition temperature observed by differential scanning calorimetry (DSC) of the polymer (2) is in the range of 50 ° C. or higher and 180 ° C. or lower. The melting peak temperature of the polymer (2) is a temperature at the top of the melting peak obtained by analyzing a melting curve measured by the following differential scanning calorimetry by a method according to JIS K7121-1987. This is the temperature at which the amount of heat is maximum.

  The glass transition temperature of the polymer (2) is an intermediate glass transition temperature obtained by analyzing a melting curve measured by the following differential scanning calorimetry by a method according to JIS K7121-1987.

[Differential scanning calorimetry]
By means of a differential scanning calorimeter, an aluminum pan encapsulating about 5 mg of sample in a nitrogen atmosphere was (1) held at 200 ° C. for 5 minutes, then (2) 200 ° C. to −50 at a rate of 5 ° C./min The temperature is then lowered to 3 ° C., then (3) held at −50 ° C. for 5 minutes, and (4) the temperature is raised from −50 ° C. to 200 ° 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.

  Examples of the polymer (2) having a melting peak temperature in the range of 50 ° C. or higher and 180 ° C. or lower include those having a structural unit derived from ethylene. Specifically, it has more than 50% of structural units derived from ethylene (however, the total amount of the structural units constituting the polymer is 100% by weight), and the melting peak temperature is in the range of 50 ° C. or higher and 180 ° C. or lower. The structural unit derived from polyethylene and propylene contained therein is more than 50% (provided that the total amount of the structural units constituting the polymer is 100% by weight), and the melting peak temperature is in the range of 50 ° C. or higher and 180 ° C. or lower. Polypropylene (PP) inside is mentioned.

  Examples of the polyethylene having a melting peak temperature in the range of 50 ° C. or higher and 180 ° C. or lower include high density polyethylene (HDPE), high pressure method low density polyethylene (LDPE), ethylene-α-olefin copolymer, and ethylene-vinyl acetate. A copolymer (EVA) is mentioned.

  Examples of the polymer (2) having a glass transition temperature in the range of 50 ° C. or higher and 180 ° C. or lower include cyclic olefin polymer (COP), cyclic olefin copolymer (COC), polystyrene (PS), and polyvinyl chloride. (PVC), acrylonitrile-styrene copolymer (AS), acrylonitrile-butadiene-styrene copolymer (ABS), polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA), polyethylene terephthalate (PET), polyacrylonitrile ( PAN), polyamide 6 (PA6), polyamide 66 (PA66), polycarbonate (PC), polyphenylene sulfide (PPS), and polyetheretherketone (PEEK).

  The ethylene-α-olefin copolymer as the polymer (2) is a copolymer having a structural unit derived from ethylene and a structural unit derived from an α-olefin. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene and 4-methyl-1-hexene. However, two or more types may be used. The α-olefin is preferably an α-olefin having 4 to 8 carbon atoms, more preferably 1-butene, 1-hexene, or 1-octene.

The density of the high-density polyethylene, high-pressure method low-density polyethylene, and ethylene-α-olefin copolymer as the polymer (2) is 860 kg / m ³ or more and 960 kg / m ³ or less.

  Examples of the polypropylene as the polymer (2) include propylene homopolymers, propylene random copolymers as described below, and propylene polymerized materials as described below. The content of the structural unit derived from propylene in the polypropylene is more than 50% by weight and 100% by weight or less (provided that the total amount of the structural units constituting the polypropylene is 100% by weight). Moreover, it is preferable that the said melting peak temperature of a polypropylene is 100 degreeC or more.

  The propylene random copolymer is a random copolymer having a structural unit derived from propylene, and at least one structural unit selected from the group consisting of a structural unit derived from ethylene and a structural unit derived from α-olefin. It is. Examples of the propylene random copolymer include a propylene-ethylene random copolymer, a propylene-ethylene-α-olefin random copolymer, and a propylene-α-olefin random copolymer. The α-olefin is preferably an α-olefin having 4 to 10 carbon atoms. Examples of such α-olefin include 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene and the like. And linear α-olefins such as 3-methyl-1-butene and 3-methyl-1-pentene. The α-olefin contained in the propylene random copolymer may be one type or two or more types.

  As a method for producing a propylene homopolymer and a propylene random copolymer, a slurry polymerization method, a solution using a known Ziegler-Natta catalyst, or a known complex catalyst such as a metallocene complex or a nonmetallocene complex is used. Known polymerization methods such as a polymerization method, a bulk polymerization method, and a gas phase polymerization method may be mentioned.

  The propylene polymerized material is a propylene homopolymer component (I), at least one structural unit selected from the group consisting of a structural unit derived from propylene and a structural unit derived from an α-olefin having 4 or more carbon atoms, and It is a polymerization material consisting of an ethylene copolymer component (II) having a structural unit derived from ethylene.

  Examples of the α-olefin having 4 or more carbon atoms in the ethylene copolymer component (II) include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1- Decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, Examples include 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, and 2,2,4-trimethyl-1-pentene. The α-olefin having 4 or more carbon atoms is preferably an α-olefin having 4 to 20 carbon atoms, more preferably an α-olefin having 4 to 10 carbon atoms, 1-butene, 1-hexene, or 1 -Octene is more preferred. The α-olefin having 4 or more carbon atoms contained in the ethylene copolymer component (II) may be one type or two or more types.

  Examples of the ethylene copolymer component (II) include propylene-ethylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, propylene-ethylene- Examples include 1-butene copolymer, propylene-ethylene-1-hexene copolymer, and propylene-ethylene-1-octene copolymer. The ethylene copolymer component (II) may be a random copolymer or a block copolymer.

The propylene polymerized material can be produced by multistage polymerization using a polymerization catalyst. For example, the propylene polymer material can be produced by producing the propylene homopolymer component (I) in the former polymerization step and producing the ethylene copolymer component (II) in the latter polymerization step.
Examples of the polymerization catalyst used for the production of the propylene polymerized material include the catalysts used for the production of a propylene homopolymer and a propylene random copolymer.

  Examples of the polymerization method in each polymerization step for producing the propylene polymerized material include a bulk polymerization method, a solution polymerization method, a slurry polymerization method, and a gas phase polymerization method. Examples of the inert hydrocarbon solvent used in the solution polymerization method and the slurry polymerization method include propane, butane, isobutane, pentane, hexane, heptane, and octane. Two or more of these polymerization methods may be combined, and may be either batch type or continuous type. The polymerization method in the production of the propylene polymerized material is preferably continuous gas phase polymerization, bulk-gas phase polymerization in which bulk polymerization and gas phase polymerization are continuously performed.

  The polypropylene as the polymer (2) is preferably a propylene homopolymer.

The polymer (2) contained in the intermediate layer (2) is a polymer having a melting peak temperature in the range of 50 ° C. or higher and 180 ° C. or lower, and preferably contains more than 50% of structural units derived from ethylene. It is a polyethylene having a melting peak temperature in the range of 50 ° C. or higher and 180 ° C. or lower (provided that the total amount of structural units constituting the polymer is 100% by weight).
The polymer (2) contained in the intermediate layer (2) may be one type or two or more types.

  In one embodiment, the intermediate layer (2) is a non-foamed layer made of non-foamed material.

  The heat storage layer (1) and the intermediate layer (2) are respectively an inorganic filler, an organic filler, an antioxidant, a weathering stabilizer, an ultraviolet absorber, a heat stabilizer, a light stabilizer, an antistatic agent, and a crystal nucleation. Additives such as agents, pigments, adsorbents, metal chlorides, hydrotalcites, aluminates, lubricants, and silicone compounds may also be included. Moreover, the additive may be contained in any one of the said thermal storage layer (1) and the said intermediate | middle layer (2), and may be contained in both.

  The amount of the additive is 0.001 part by weight or more and 10 parts by weight per 100 parts by weight of the resin composition constituting the heat storage layer (1) and 100 parts by weight of the resin composition constituting the intermediate layer (2). The amount is preferably not more than parts by weight, more preferably not less than 0.005 parts by weight and not more than 5 parts by weight, and still more preferably not less than 0.01 parts by weight and not more than 1 part by weight.

  When the heat storage layer (1) contains an additive, the additive may be blended in advance with one or more raw materials used during the production of the polymer (1). You may mix | blend after manufacturing. Moreover, you may mix | blend this additive previously with one or more raw materials used at the time of manufacture of the said polymer (2), and you may mix | blend after manufacturing the said polymer (2). Furthermore, you may mix | blend with the said polymer (1) and the said polymer (2), and you may mix | blend this additive with both. When the additive is added to the polymer after producing the polymer (1), the additive can be added while the polymer is melt-kneaded. Moreover, after manufacturing the said polymer (2), when mix | blending an additive with this polymer, an additive can be mix | blended, melt-kneading a polymer.

  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 thickness of the intermediate layer (2) is usually 1 μm or more and 1 mm or less, preferably 10 μm or more and 100 μm or less.

<Base material layer (3)>
The laminate of the present invention has a base material layer (3) made of paper. The base material layer (3) is adjacent to the intermediate layer (2).

  Examples of the base material made of paper include cast-coated paper, art paper, coated paper, craft paper, high-quality paper, synthetic paper, and the like, and can be appropriately used depending on the application and purpose.

  The thickness of the base material layer (3) is usually from 1 μm to 1 mm, preferably from 10 μm to 100 μm.

[2. Manufacturing method of laminate]
The laminated body of one Embodiment is the process of heat-bonding the molded object which has the said thermal storage layer (1), and the intermediate | middle layer (2) of the molded object which has the said intermediate | middle layer (2) and the said base material layer (3). It is obtained by the manufacturing method containing.

  In one embodiment, the laminate of the present invention is a step of preparing a molded body having the heat storage layer (1), and a step of preparing a molded body having the intermediate layer (2) and the base material layer (3). And a step of heat-bonding the molded body having the heat storage layer (1) and the intermediate layer (2) of the molded body having the intermediate layer (2) and the base material layer (3). .

<Molded body having heat storage layer (1)>
In one Embodiment, the molded object which has a thermal storage layer (1) is a sheet form.
When the molded body is in the form of a sheet, in the step of preparing the molded body having the heat storage layer (1), the sheet having the heat storage layer (1) is made from the resin composition constituting the heat storage layer (1). Obtained by molding. 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.

<Molded body having the intermediate layer (2) and the base material layer (3)>
In one Embodiment, the molded object which has the said intermediate | middle layer (2) and base material layer (3) is a sheet form.
When the molded body is in the form of a sheet, in the step of preparing the molded body having the intermediate layer (2) and the base material layer (3), the sheet having the intermediate layer (2) and the base material layer (3) is For example, the intermediate layer (2) can be obtained by extrusion lamination molding on one side of the base material layer (3). As an apparatus for extrusion laminating, an ordinary T-die type apparatus can be used. There is no restriction | limiting in particular in the thickness of a laminate, What is necessary is just to select the thickness according to the objective suitably.

  As a step of heat bonding the molded body having the heat storage layer (1) and the intermediate layer (2) of the molded body having the intermediate layer (2) and the base material layer (3), the heat storage layer (1 ) And a molded body having the intermediate layer (2) and the base material layer (3) are superimposed on the surface of the intermediate layer (2), and an iron or the like is applied from the surface of the base material layer (3). The process of heat-bonding with the heated jig | tool is mentioned.

  When the molded body is in the form of a sheet, as a step of heat bonding the sheet having the heat storage layer (1) and the intermediate layer (2) of the sheet having the intermediate layer (2) and the base material layer (3) The sheet having the heat storage layer (1) and the sheet having the intermediate layer (2) and the base layer (3) are overlapped on the surface of the intermediate layer (2), and the base layer (3) The process of heat-bonding with the heated jigs, such as an iron, from the surface is mentioned.

  As one aspect of the use form of the laminate of the present invention, use between a gypsum board in a general wall material and wallpaper is mentioned. Moreover, use as a ceiling material or a flooring is also mentioned as a usage form of the laminated body of this invention.

  The laminate of the present invention is adjacent to the heat storage layer (1) only on one side of the heat storage layer (1), and comprises the intermediate layer (2) made of the polymer (2) and the intermediate layer (2). And having a base material layer (3) made of paper, the construction method of the laminate in the usage form for use between the gypsum board in the wall material and the wallpaper is gypsum. The board and the laminate are overlapped on the surface of the heat storage layer (1) of the laminate, and the heat storage layer (1) is fixed to the gypsum board with a tucker or a screw, and then the base layer (3) in general. A method of applying a typical building material adhesive and further laminating wallpaper.

  Moreover, the laminated body of this invention is adjacent to the said thermal storage layer (1) on both surfaces of a thermal storage layer (1), The intermediate | middle layer (2) which consists of the said polymer (2), and the said intermediate | middle layer (2 ), And having a base material layer (3) made of paper, as a construction method of the laminate in a use form for use between the gypsum board in the wall material and the wallpaper, A general building material adhesive is applied to the gypsum board, the base material layer (3) of the laminate is laminated on the surface, the base material layer (3) is fixed, and then the other base material layer ( There is a method of applying a general building material adhesive to 3) and further laminating wallpaper.

  In addition, the laminate of the present invention can be colored by adding a pigment when applied to the outermost layer of the wall, for example, when a laminate is applied directly under the wallpaper, when a thumbtack, a nail or a tucker is used on the wallpaper. And there is no fear that paraffin leaks like the conventional paraffin heat storage material. Thus, the laminated body of this invention is excellent in adhesiveness with wallpaper, and can be used suitably as a building material.

  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 the composed polymer (1), the ¹³ C-NMR spectrum of the polymer obtained according to ¹³ C NMR measurement conditions described above, the following _{f 1} and scope of _{g 1} The integral value of was obtained. Next, from the following formula, the structural unit (C ₁ ) derived from methyl acrylate contained in the ethylene-methyl acrylate copolymer is a structural unit (B ₂ ) represented by the formula (1) of the polymer (1). The conversion rate (X ₁ ) converted to 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 (1), structural units derived from ethylene _(A 2), the structural unit represented by the formula (1) _(B 2), the number of structural units derived from methyl acrylate _{(C 2)>} ( unit:%) contained in the polymer (1), structural units derived from ethylene _(a 2), the constituent unit _(B 2 represented by the formula (1)), the structural units of _{(C 2)} derived from methyl acrylate The numbers were calculated from the following formulas.
Number of structural units (A ₂ ) contained in polymer (1) = number of structural units (A ₁ ) contained in ethylene-methyl acrylate copolymer of structural units (B ₂ ) contained in polymer (1) Number = (number of structural units (C ₁ ) contained in the ethylene-methyl acrylate copolymer) × conversion rate (X ₁ ) / 100
Number of structural units (C ₂ ) contained in polymer (1) = (Number of structural units (C ₁ ) contained in ethylene-methyl acrylate copolymer) − (Structural units contained in polymer (1) ( the number of B ₂₎₎

<Number of structural units derived from ethylene (A ₃ ) and structural units derived from α-olefin (B ₃ ) contained in the ethylene-α-olefin copolymer> (unit:%)
About the ¹³ C-NMR spectrum of the ethylene-α-olefin copolymer obtained according to the above ¹³ C-NMR measurement conditions, the following a ₃ , b ₃ , c ₃ , d ₃ , d ′ ₃ , e ₃ , f ₃ , g ₃ , h ₃ , i _3, and j _{3 in} the range of integral values, including eight triads (EEE, EEL, LEE, LEL, ELE, ELL, LLE, LLL) obtained from the following formula From the amount (number), the number of structural units derived from ethylene (A ₃ ) and structural units derived from α-olefin (B ₃ ) was calculated. In each triad, E represents ethylene and L represents α-olefin.

a ₃ : 40.6-40.1 ppm
b _3: 38.5-38.0 ppm
c _3: 36.3-35.8 ppm
d _3: 35.8-34.3 ppm
d ′ ₃ : 34.0-33.7 ppm
e ₃ : 32.4-31.8 ppm
f _3: 31.4-29.1 ppm
g _3: 27.8-26.5 ppm
h _3: 24.8-24.2 ppm
i ₃ : 23.0-22.5 ppm
j ₃ : 14.4-13.6 ppm

EEE = f ₃ / 2−g ₃ / 4− (n _L −7) × (b ₃ + c ₃ + d ′ ₃ ) / 4
EEL + LEE = g ₃ −e ₃
LEL = h ₃
ELE = b ₃
ELL + LLE = c _{3
LLL = a 3 -c 3/2} ( when _{a 3 -c 3/2 <0} , LLL = d '3)
The above n _L represents the average number of carbon atoms of the α-olefin.

Number of structural units (A ₃ ) = 100 × (EEE + EEL + LEE + LEL) / (EEE + EEL + LEE + LEL + ELE + ELL + LLE + LLL)
Number of structural units (B ₃ ) = 100−number of structural units (A ₃ )

[II] Content of unreacted compound having an alkyl group having 14 to 30 carbon atoms (unit:% by weight)
In “production of polymer (1)” in each example, the product obtained is a mixture of the polymer (1) 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 (1) 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./min, 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) Preparation of calibration curve [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 the 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) (1) Melting peak temperature (T _m , unit: ° C.) Melting enthalpy (ΔH, unit: J / J) observed within a temperature range of 10 ° C. or more and less than 60 ° C. g)
Using a differential scanning calorimeter (TA Instruments, DSCQ100), 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./minute. The temperature was lowered from 150 ° C. to −50 ° C. at a rate of (3), then held at −50 ° C. for 5 minutes, and then (4) the temperature was raised from −50 ° C. to about 150 ° C. at a rate of 5 ° C./min. . 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 values of the polymer (1) and the polyethylene reference material 1475a (manufactured by National Institute of Standards and Technology) Molecular weight and intrinsic viscosity were 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: about 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 plots the measured data with the logarithm of the absolute molecular weight of the polymer (1) as the horizontal axis and the logarithm of the intrinsic viscosity of the polymer (1) as the vertical axis, and the logarithm of the absolute molecular weight and the logarithm of the intrinsic viscosity are In the range where the horizontal axis is not less than the logarithm of the weight average molecular weight of the polymer and not more than 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 expressed. It is a value obtained by a method including setting α ₁ .
log [η ₁ ] = α ₁ logM ₁ + logK ₁ (I−I)
(In the formula (II), [η ₁ ] represents the intrinsic viscosity (unit: dl / g) of the polymer (1), 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] 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: 87.1% (68.8% by weight), number of structural units derived from methyl acrylate: 12.9% (31.2% by weight), MFR (at 190 ° C., 21 N) Measurement): 40.5 g / 10 min

<Compound having an alkyl group having 14 to 30 carbon atoms>
B-1: Calcoal 6098 (n-hexadecyl alcohol) [manufactured by Kao Corporation]
B-2: Calcoal 8098 (n-octadecyl alcohol) [manufactured by Kao Corporation]
B-3: n-octadecyl methacrylate [manufactured by Tokyo Chemical Industry Co., Ltd.]

<Catalyst>
C-1: Tetra orthotitanate (n-octadecyl) [Matsumoto Fine Chemical Co., Ltd.]

<Olefin polymer>
D-1: Sumitomo Nobrene D101 (propylene homopolymer, melting point 163 ° C.) [manufactured by Sumitomo Chemical Co., Ltd.]
D-2: Sumikasen L705 (high-pressure low-density polyethylene, melting point 106 ° C.) [manufactured by Sumitomo Chemical Co., Ltd.]

<Organic peroxides and azo compounds>
E-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 Co., Ltd.]
E-2: YP-50S (a mixture comprising 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, amorphous silicon dioxide, amorphous silica, and liquid paraffin) (1 minute (Half-life temperature: 180 ° C) [manufactured by Kayaku Akzo Corporation]
E-3: Azobisisobutyronitrile (10 hour half-life temperature: 65 ° C.) [manufactured by Tokyo Chemical Industry Co., Ltd.]

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

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

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

<Processing machine>
Twin screw extruder (1)
・ Barrel diameter D = 75mm
・ Screw effective length L / barrel diameter D = 40
Twin screw extruder (2)
・ Barrel diameter D = 15mm
・ Screw effective length L / barrel diameter D = 45
Coextrusion laminator (1)
・ Barrel diameter D = 65mm
・ Screw effective length L / barrel diameter D = 32

[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: 73.6 parts by weight, C-1: 0.8 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 polypropylene homopolymer) Obtained in Reference Example 1 (1) Polymer (cf1): 80 parts by weight, D-1: 20 parts by weight, E-1: 1.0 part by weight, F-1: 1.0 part by weight, G-1: 0.1 Part by weight and H-1: 0.1 part by weight using a twin screw extruder (1), screw rotation speed 350 rpm, discharge rate 200 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.
(2) Production of heat storage layer The crosslinked resin composition (cf2) obtained in Reference Example 2 (1) was compression molded at 200 ° C. for 10 minutes using a mold having a cavity size of 50 mm × 50 mm × 3 mm. And the thermal storage layer (cf2) which consists of a sheet | seat of the resin composition (cf2) bridge | crosslinked by cutting as needed was obtained.
Thermal storage layer: 50mm x 50mm x 3mm

[Reference Example 3]
(1) Manufacture of a polymer (ethylene-α-olefin copolymer) comprising the structural unit (A) and the structural unit (B) After drying under reduced pressure, the inner volume of the autoclave with a stirrer is replaced by nitrogen. 1.4L of toluene solution containing 706 g of α-olefin C2024 (olefin mixture of 18, 20, 22, 24, 26 carbon atoms, manufactured by Ineos Co.) is added, and then toluene is added so that the liquid volume becomes 3L. Was added. After raising the temperature of the autoclave to 60 ° C., ethylene was added so that the partial pressure became 0.1 MPa, and the inside of the system was stabilized. A hexane solution of triisobutylaluminum (0.34 mol / L, 14.7 ml) was added thereto. Next, a toluene solution of dimethylanilinium tetrakis (pentafluorophenyl) borate (1.0 mmol / 13.4 mL), a toluene solution of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride (0.2 mmol / L, 7 .5 mL) was added to initiate polymerization, and ethylene gas was fed so as to keep the total pressure constant.
After 3 hours, 2 ml of ethanol was added to terminate the polymerization. After the polymerization was stopped, a toluene solution containing the polymer was added to acetone to precipitate the ethylene-α-olefin copolymer (cf3), and the filtered polymer (cf3) was further washed twice with acetone. did.
The obtained polymer (cf3) was vacuum dried at 80 ° C. to obtain 369 g of the polymer (cf3). Table 1 shows the physical property values and evaluation results of the polymer (cf3).

[Reference Example 4]
(1) Production of Crosslinked Resin Composition (Resin Composition Comprising Crosslinked Ethylene-α-Olefin Copolymer and Polypropylene Homopolymer) Polymer Obtained in Reference Example 3 (1) (cf3) ): 80 parts by weight, D-1: 20 parts by weight, E-2: 0.5 parts by weight, F-1: 0.75 parts by weight, G-1: 0.1 parts by weight Extruded at a screw speed of 150 rpm, a discharge rate of 1.8 kg / hr, a barrel first half temperature of 180 ° C., a barrel second half temperature of 220 ° C., and a die temperature of 200 ° C. using a shaft extruder (2), and a crosslinked resin composition A product (cf4) was produced.
(2) Production of heat storage layer The crosslinked resin composition (cf4) obtained in Reference Example 4 (1) was compression molded at 200 ° C. for 10 minutes using a mold having a cavity size of 50 mm × 50 mm × 3 mm. And the thermal storage layer (cf4) which consists of a sheet | seat of the resin composition (cf4) bridge | crosslinked by cutting as needed was obtained.
Thermal storage layer: 50mm x 50mm x 3mm

[Reference Example 5]
(1) Production of polymer consisting of structural unit (B) (n-octadecyl methacrylate homopolymer) After drying under reduced pressure, B-3: 126.7 g was added to a 300 mL flask whose internal volume was replaced with nitrogen, The internal temperature was set to 50 ° C., and the mixture was heated and stirred to completely dissolve B-3. Subsequently, E-3: 307.3 mg was added, the internal temperature was set to 80 ° C., the mixture was heated and stirred for 80 minutes, and the product was washed with 1000 mL of ethanol and vacuum-dried at 120 ° C. to obtain a polymer (cf5). (N-octadecyl methacrylate homopolymer) was obtained. Table 1 shows the physical property values and evaluation results of the polymer (cf5).

[Reference Example 6]
(1) Preparation of resin composition (resin composition containing n-octadecyl methacrylate homopolymer and polypropylene homopolymer) Resin composition (cf5) obtained in Reference Example 5 (1): 80 parts by weight and D- 2:20 parts by weight was kneaded in a lab plast mill (model 65C150, manufactured by Toyo Seiki Seisakusho Ltd.) under a nitrogen atmosphere at a rotation speed of 80 rpm and a chamber temperature of 200 ° C. for 5 minutes to prepare a resin composition (cf6).
(2) Production of heat storage layer The crosslinked resin composition (cf6) obtained in Reference Example 6 (1) was compression molded at 200 ° C. for 10 minutes using a mold having a cavity size of 50 mm × 50 mm × 3 mm. And the thermal storage layer (cf6) which consists of a sheet | seat of the resin composition (cf6) bridge | crosslinked by cutting as needed was obtained.
Thermal storage layer: 50mm x 50mm x 3mm

[Reference Example 7]
(1) Production of a laminate having an intermediate layer made of high-pressure low-density polyethylene and a base material layer made of kraft paper Using a coextrusion laminator (1), the discharge rate is 70 to 80 kg / hr, and the line speed is 200 to 300 m. / Min, cooling roll temperature: 20 ° C., barrel first half temperature 220 ° C., barrel second half temperature 330 ° C., die temperature 330 ° C. Extruded molten D-2 onto kraft paper (50 g / m ² ) The obtained laminate having an intermediate layer made of high-pressure process low-density polyethylene and a base material layer made of kraft paper was cut into the following sizes to produce a laminate (cf7).
Laminated body having an intermediate layer made of high-pressure low-density polyethylene and a base material layer made of kraft paper: 50 mm × 50 mm

[Reference Example 8]
(1) Preparation of laminate having intermediate layer made of polypropylene homopolymer and base material layer made of kraft paper Laminate having intermediate layer made of polypropylene homopolymer and base material layer made of kraft paper (Nippon Matai Co., Ltd.) Manufactured) was cut into the following size to produce a laminate (cf8).
Laminated body having an intermediate layer made of polypropylene homopolymer and a base material layer made of kraft paper: 50 mm × 50 mm

[Reference Example 9]
(1) Production of base material layer made of kraft paper Kraft paper (50 g / m ² ) was cut into the following sizes to produce a base material layer (cf 9) made of kraft paper.
Base material layer made of kraft paper: 50mm x 50mm

[Example 1]
(1) Manufacture of laminated body It consists of a heat storage layer (cf2) obtained in (2) of Reference Example 2, an intermediate layer made of the high-pressure low-density polyethylene obtained in (1) of Reference Example 7 and kraft paper. The laminate (cf7) having the base material layer is superposed so that the intermediate layer faces the heat storage layer and the four corners are aligned, and is heated and bonded with an iron heated to 180 ° C., whereby the laminate (ex1) is obtained. Obtained.

(2) Evaluation of Adhesiveness of Laminate Grasping the corners of the laminate (cf7) constituting the laminate (ex1) obtained in (1) of Example 1, and storing the heat storage layer (cf2) in the direction of 180 ° I peeled it off. The laminate (ex1) was firmly fused, and the base material layer made of kraft paper was broken.

[Example 2]
(1) Production of Laminate A laminate (cf7) having an intermediate layer made of high-pressure low-density polyethylene obtained in (1) of Reference Example 7 and a base material layer made of kraft paper (1) of Reference Example 8 Except for changing to a laminate (cf8) having an intermediate layer made of polypropylene homopolymer and a base material layer made of kraft paper, the laminate ( ex2) was obtained.

(2) Evaluation of Adhesiveness of Laminate Except for changing the laminate (ex1) obtained in (1) of Example 1 to the laminate (ex2) obtained in (1) of Example 2, It peeled off like Example 1 (2). The laminate (ex2) was firmly fused, and the base material layer made of kraft paper was broken.

Example 3
(1) Production of Laminate Example, except changing the heat storage layer (cf2) obtained in (2) of Reference Example 2 to the heat storage layer (cf4) obtained in (2) of Reference Example 4 1 (1) was performed to obtain a laminate (ex3).

(2) Adhesive evaluation of laminated body Except changing the laminated body (ex1) obtained in (1) of Example 1 to the laminated body (ex3) obtained in (1) of Example 3, It peeled off like Example 1 (2). The laminate (ex3) was firmly fused, and the base material layer made of kraft paper was broken.

Example 4
(1) Production of Laminate A laminate (cf7) having an intermediate layer made of high-pressure low-density polyethylene obtained in (1) of Reference Example 7 and a base material layer made of kraft paper (1) of Reference Example 8 The same procedure as in Example 3 (1) except that the laminate (cf8) has an intermediate layer made of a polypropylene homopolymer obtained in (1) and a base material layer made of kraft paper. ex4) was obtained.

(2) Adhesive evaluation of laminated body Except changing the laminated body (ex1) obtained in (1) of Example 1 to the laminated body (ex4) obtained in (1) of Example 4, It peeled off like Example 1 (2). The laminate (ex4) was firmly fused, and the base material layer made of kraft paper was broken.

Example 5
(1) Production of Laminate Example, except changing the heat storage layer (cf2) obtained in (2) of Reference Example 2 to the heat storage layer (cf6) obtained in (2) of Reference Example 6 2 (1) was performed to obtain a laminate (ex5).

(2) Evaluation of Adhesiveness of Laminate Except for changing the laminate (ex1) obtained in (1) of Example 1 to the laminate (ex5) obtained in (1) of Example 5, It peeled off like Example 1 (2). The laminate (ex5) was firmly fused, and the base material layer made of kraft paper was broken.

[Comparative Example 1]
(1) Production of Laminate A laminate (cf7) having an intermediate layer made of high-pressure low-density polyethylene obtained in (1) of Reference Example 7 and a base material layer made of kraft paper (1) of Reference Example 9 The laminate (ref1) was obtained in the same manner as in Example 1 (1) except that the base material layer (cf9) made of kraft paper obtained in (1) was changed.

(2) Adhesive evaluation of laminated body The corner | angular part of the base material layer of the laminated body (ref1) obtained by (1) of the comparative example 1 was grasped, and it peeled off from the thermal storage layer in the direction of 180 degrees. The base material layer peeled from the heat storage layer without breaking.

[Comparative Example 2]
(1) Production of Laminate A laminate (cf7) having an intermediate layer made of high-pressure low-density polyethylene obtained in (1) of Reference Example 7 and a base material layer made of kraft paper (1) of Reference Example 9 The laminate (ref2) was obtained in the same manner as in Example 3 (1) except that the substrate layer was changed to the base material layer (cf9) made of kraft paper.

(2) Adhesive evaluation of laminated body The corner | angular part of the base material layer of the laminated body (ref2) obtained by (1) of the comparative example 2 was grasped, and it peeled off from the thermal storage layer in the direction of 180 degrees. The base material layer peeled from the heat storage layer without breaking.

  The present invention can be used as a building material such as a wall material.

Claims (9)

A heat storage layer (1) comprising a 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,
A polymer adjacent to the heat storage layer (1) and having a melting peak temperature or a glass transition temperature of 50 ° C. or higher and 180 ° C. or lower observed by differential scanning calorimetry (however, excluding the polymer (1)). An intermediate layer (2) comprising the union (2), and
Substrate layer (3) made of paper adjacent to the intermediate layer (2)
A laminate having The heat storage layer (1) contains the polymer (1) and the polymer (2),
When the total amount of the polymer (1) and the polymer (2) is 100% by weight, the content of the polymer (1) is 30% by weight to 99% by weight, and the polymer ( The laminate according to claim 1, wherein the content of 2) is 1% by weight or more and 70% by weight or less. The polymer (1) has a structural unit (A) derived from ethylene and a structural unit (B) represented by the following formula (1), and a structural unit represented by the following formula (2) and the following formula: It may have at least one structural unit (C) selected from the group consisting of structural units represented by (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 laminate according to claim 1, wherein the polymer is a polymer having 0% to 99%.

(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. And 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 is 100%. Item 4. The laminate according to Item 3. The laminate A 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 laminate (1) according to any one of claims 1 to 5, wherein the polymer (1) is a crosslinked polymer.   The laminate according to any one of claims 1 to 6, wherein the gel fraction of the polymer (1) is 20% by weight or more (provided that the weight of the polymer (1) is 100% by weight).   The laminate (1) according to any one of claims 1 to 7, wherein the polymer (2) is a polymer containing a structural unit derived from ethylene. A molded body having the heat storage layer (1);
The manufacturing method of the laminated body as described in any one of Claims 1-8 including the process of heat-bonding the intermediate | middle layer (2) of the molded object which has the said intermediate | middle layer (2) and the said base material layer (3). .