CN114132026A

CN114132026A - Composite sheet

Info

Publication number: CN114132026A
Application number: CN202010917648.0A
Authority: CN
Inventors: 尹起忠; 丁军义; 德山英幸; 孙超
Original assignee: Nitto Denko Shanghai Songjiang Co Ltd; Nitto Denko Corp
Current assignee: Nitto Denko Shanghai Songjiang Co Ltd; Nitto Denko Corp
Priority date: 2020-09-03
Filing date: 2020-09-03
Publication date: 2022-03-04

Abstract

The present invention relates to a composite sheet. The composite sheet of the present invention comprises: temperature control layer, setting are in the first substrate layer of the first side on temperature control layer and setting are in the second substrate layer of the second face on temperature control layer, compound piece still includes at least one end liner layer, the end liner layer set up in temperature control layer with between the first substrate layer and/or temperature control layer with between the second substrate layer, the temperature control layer contains phase change material and adhesive, the phase transition heat absorption enthalpy value of compound piece is 95 ~ 200J/g. The composite sheet has high phase change heat absorption enthalpy value, is not easy to damage, has high cycle use times, can effectively prevent glue overflow in the use process, and greatly improves the operability and the production efficiency.

Description

Composite sheet

Technical Field

The invention relates to a composite sheet, in particular to a composite sheet which has high phase change heat absorption enthalpy value, is not easy to damage, has high recycling times and can effectively prevent glue overflow in the using process.

Background

In recent years, electrochemical devices such as batteries (in particular, nonaqueous batteries such as lithium ion batteries) have been widely used as components constituting electronic circuits. With the rapid development of the electronic, information and communication industries, electronic products are developing to be short, small, light and thin, and the requirements for the thermal management technology of each component of the electronic circuit are becoming more and more strict.

In recent years, rapid development of phase change materials, which are materials that change physical properties with temperature change and realize absorption or release of heat, provides a new idea for improving high and low temperature performance of electronic components. The energy storage diaphragm is made of the phase-change material, energy supply can be realized by absorbing or releasing heat, the effect of properly cooling or preserving heat of an electronic product along with the change of external temperature can be achieved, and the balance between temperature change and energy supply is realized.

However, the conventional energy storage membrane made of the phase-change energy storage material has the defects of thick thickness (for example, more than 100 μm), low heat absorption enthalpy per unit volume, low cycle use frequency (within 30 times), easy breakage, easy glue overflow of products under high temperature and high pressure, pollution to electrode electronic components and the like. In addition, the thickness of the material is thick, so that the material is not in line with the development trend of light and thin electronic instruments and equipment. Moreover, the production operability and the production efficiency are greatly reduced.

Disclosure of Invention

Problems to be solved by the invention

The present invention has been made to solve the above-mentioned conventional problems, and an object of the present invention is to provide a composite sheet which has a thin thickness, a high phase-change enthalpy value of heat absorption, a high cycle number (30 times or more), and a remarkably improved glue overflow phenomenon during use, thereby greatly improving workability and production efficiency.

Means for solving the problems

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by specifically constructing the structure and composition of a composite sheet and controlling the phase change endothermic enthalpy of the composite sheet within a specific range, and have completed the present invention.

Namely, the present invention is as follows.

[1] A composite sheet, comprising: a temperature control layer, a first base material layer arranged on the first surface of the temperature control layer, and a second base material layer arranged on the second surface of the temperature control layer,

the composite sheet also comprises at least one bottom lining layer which is arranged between the temperature control layer and the first base material layer and/or between the temperature control layer and the second base material layer,

the temperature control layer comprises a phase change material and a binder,

the phase change heat absorption enthalpy value of the composite sheet is 95-200J/g.

[2] The composite sheet according to [1], wherein the temperature control layer comprises:

a phase change region formed from a temperature control composition comprising a first binder and a first phase change material; and

an adhesive region formed from an adhesive composition comprising a second adhesive,

the phase change regions and the adhesive regions are arranged in an alternating manner in a Transverse Direction (TD) of the temperature control layer, the transverse direction being perpendicular to the processing direction of the composite sheet, and the area ratio of the adhesive regions to the phase change regions is 0: 1-10: 1.

[3] The composite sheet according to [2], wherein the adhesive region contains a second phase change material, and the content of the second phase change material in the adhesive region is 0 to 20 mass%, preferably 5 to 15 mass%.

[4] The composite sheet according to any one of [1] to [3], wherein the composite sheet has a phase transition enthalpy value of 120 to 200J/g;

preferably, the thickness of the composite sheet is 70-100 μm;

preferably, the thickness of the temperature control layer is 40-80 μm, preferably 50-70 μm;

preferably, the thickness of the bottom lining layer is 1-5 μm, and preferably 1-3 μm.

[5]According to [1]～[3]The composite sheet of any one of the above, wherein the first and second substrate layers have a density of 1.4g/cm³The following;

preferably, the heat conduction coefficient of the first base material layer is 0.15-0.6W/M.K;

preferably, the thickness of the first base material layer is 2-12 μm, preferably 2-6 μm;

preferably, the heat conduction coefficient of the second base material layer is 0.15-0.6W/M.K;

preferably, the thickness of the second substrate layer is 2-12 μm, and preferably 2-6 μm.

[6] The composite sheet according to [2], wherein the thickness of the adhesive region is 40 to 80 μm, preferably 50 to 70 μm;

preferably, the width of the adhesive area is 2-10 mm, preferably 2-8 mm;

preferably, the thickness of the phase change region is 40-80 μm, preferably 50-70 μm;

preferably, the width of the phase change region is 40-200 mm, and preferably 100-150 mm.

[7] The composite sheet according to [2], wherein the first adhesive has a bleed width of 1mm or less under a condition of 150 ℃x0.1 MPa x 1H;

preferably, the second adhesive has a glue overflow width of less than 1mm under the conditions of 150 ℃ multiplied by 0.1MPa multiplied by 1H;

preferably, the adhesive force of the first adhesive after 10 seconds at 85 ℃ and 0.1MPa is 1.0-20N/10 mm, preferably 3.0-20N/10 mm, and more preferably 5.0-20N/10 mm;

preferably, the adhesive force of the second adhesive after 10 seconds at 85 ℃ and 0.1MPa is 1.0-20N/10 mm, preferably 3.0-20N/10 mm, and more preferably 5.0-20N/10 mm.

[8] The composite sheet according to [2], wherein the first adhesive comprises a hot melt adhesive;

preferably, the second adhesive comprises a hot melt adhesive;

preferably, the first binder has a density of 1.0g/cm³The following;

preferably, the second binder has a density of 1.0g/cm³The following;

preferably, the first binder has a melt index at a temperature of 230 ℃ under a load of 5kg of 10g/min or less;

preferably, the second binder has a melt index of 10g/min or less at a temperature of 230 ℃ and a load of 5 kg.

[9] The composite sheet according to [2], wherein the phase change material in the temperature control layer comprises graft modified phase change energy storage particles,

preferably, the phase change temperature of the graft modified phase change energy storage particles is 30-50 ℃, and preferably 35-45 ℃;

preferably, the particle size distribution of the graft modified phase change energy storage particles is 2-100 μm, and the content of the graft modified phase change energy storage particles with the particle size distribution of less than 10 μm in all the graft modified phase change energy storage particles is less than 10 vol%;

preferably, the phase change enthalpy value of the grafting modified phase change energy storage particle is more than 190J/g,

preferably, the mass percentage of the graft modified phase change energy storage particles in the phase change region is 75-95%, and preferably 80-90%.

[10] The composite sheet according to any one of [1] to [3], wherein the anchoring force between the temperature control layer and the first substrate layer is 1.0 to 20N/10mm, and the anchoring force between the temperature control layer and the second substrate layer is 1.0 to 20N/10 mm;

preferably, the interlayer strength of the temperature control layer is 1.0-20.0N/10 mm.

ADVANTAGEOUS EFFECTS OF INVENTION

The composite sheet of the invention can realize high phase change heat absorption enthalpy value even with thin thickness, remarkably improve the cycle use frequency (durability), inhibit the generation of glue overflow phenomenon, greatly improve the operability and the production efficiency, and play an important role in improving the comprehensive performance of the field (such as a battery).

Drawings

Fig. 1 is a sectional view schematically showing the structure of a composite sheet according to an embodiment of the present invention.

Fig. 2 is a sectional view schematically showing the structure of a composite sheet according to another embodiment of the present invention.

Fig. 3 is a sectional view schematically showing the structure of a composite sheet according to still another embodiment of the present invention.

Fig. 4 is a cross-sectional view in the Transverse Direction (TD) schematically illustrating a temperature control layer of the composite sheet of the present invention.

Fig. 5 is a cross-sectional view schematically showing a Transverse Direction (TD) of a composite sheet according to an embodiment of the present invention.

Fig. 6 is a schematic view showing the Machine Direction (MD) and the Transverse Direction (TD) of the composite sheet of the present invention.

Description of the reference numerals

Composite sheet 100

First substrate layer 10

Second substrate layer 20

Temperature control layer 30

First substrate layer 40

Second substrate layer 50

Adhesive area 3

Phase change region 4

The edge 31 of the adhesive area

The edge 41 of the phase change region

Detailed Description

Hereinafter, preferred embodiments of the present invention will be described. Matters necessary for carrying out the present invention other than those specifically mentioned in the present specification can be understood by those skilled in the art based on the teaching about the implementation of the invention described in the present specification and the technical common general knowledge at the time of application. The present invention can be implemented based on the contents disclosed in the present specification and the technical common knowledge in the field.

In the following drawings, members and portions that exhibit the same function are sometimes described with the same reference numerals, and redundant description may be omitted or simplified. The embodiments shown in the drawings are illustrated for clarity of the present invention, and do not necessarily accurately represent the dimensions and scale of the product actually provided. Furthermore, although terms such as "top," "bottom," "upper," "lower," "above," "below," "front," "back," "first," and "second," may be used herein, it is to be understood that these terms are used in their relative sense only, unless otherwise specified.

< composite sheet >

The composite sheet of the present invention comprises: temperature control layer, setting are in the first substrate layer of the first side on temperature control layer and setting are in the second substrate layer of the second face on temperature control layer, compound piece still includes at least one end liner layer, the end liner layer set up in temperature control layer with between the first substrate layer and/or temperature control layer with between the second substrate layer, the temperature control layer contains phase change material and adhesive, the phase transition heat absorption enthalpy value of compound piece is 95 ~ 200J/g.

In the invention, the phase change heat absorption enthalpy value of the composite sheet is 95-200J/g, and preferably 120-200J/g. By enabling the phase change heat absorption enthalpy value of the composite sheet to meet the specific range, the composite sheet can realize high phase change heat absorption enthalpy value even if the composite sheet has a thin thickness, the recycling frequency is improved, the generation of glue overflow phenomenon can be inhibited, and the operability and the production efficiency are greatly improved. The phase transition endothermic enthalpy value can be measured, for example, by the method described in the examples described later.

If the phase change heat absorption enthalpy value of the composite sheet is less than 95J/g, the phase change heat absorption is less, so that heat accumulation in the production process of electronic components is caused, the yield is reduced, or the final product is abnormal in use. If the phase change heat absorption enthalpy value of the composite sheet is greater than 200J/g, the addition amount of phase change energy storage particles is large, the bonding force between the temperature control layer and the bottom lining layer or the base material layer is reduced, the composite sheet is easy to damage, the number of times of recycling is reduced, and the composite sheet is easy to overflow glue to pollute electronic components at high temperature and high pressure.

In some preferred embodiments, the composite sheet has a thickness of 70 to 100 μm, preferably 70 to 90 μm. In the present invention, even if the composite sheet has a small thickness, a high phase transition enthalpy value can be achieved, a long cycle life (durability) can be achieved, and the occurrence of flash can be effectively suppressed.

Fig. 1 is a sectional view schematically showing the structure of a composite sheet according to an embodiment of the present invention. As shown in fig. 1, the composite sheet 100 includes a temperature control layer 30, a first substrate layer 10 disposed on a first surface of the temperature control layer 30, a second substrate layer 20 disposed on a second surface of the temperature control layer 30, and a first substrate layer 40 disposed between the temperature control layer 30 and the first substrate layer 10.

Fig. 2 is a sectional view schematically showing the structure of a composite sheet according to another embodiment of the present invention. As shown in fig. 2, the composite sheet 100 includes a temperature control layer 30, a first substrate layer 10 disposed on a first surface of the temperature control layer 30, a second substrate layer 20 disposed on a second surface of the temperature control layer 30, and a second substrate layer 50 disposed between the temperature control layer 30 and the second substrate layer 20.

Fig. 3 is a sectional view schematically showing the structure of a composite sheet according to still another embodiment of the present invention. As shown in fig. 3, the composite sheet 100 includes a temperature control layer 30, a first base material layer 10 disposed on a first surface of the temperature control layer 30, a second base material layer 20 disposed on a second surface of the temperature control layer 30, a first base lining layer 40 disposed between the temperature control layer 30 and the first base material layer 10, and a second base lining layer 50 disposed between the temperature control layer 30 and the second base material layer 20.

The composite sheet of the present invention will be described in detail below.

[ temperature-controlling layer ]

The temperature control layer includes: a phase change region formed from a temperature control composition comprising a first binder and a first phase change material; and an adhesive region formed from an adhesive composition comprising a second adhesive.

In the present invention, the phase change regions and the adhesive regions are arranged alternately in a Transverse Direction (TD) of the temperature control layer, which is perpendicular to a Machine Direction (MD) of the composite sheet. In some preferred embodiments, the phase change regions and the adhesive regions are preferably alternately arranged in such a manner that a distance between adjacent phase change regions and adhesive regions is 0 to 5 mm. More preferably, in the present invention, the phase change regions and the adhesive regions are alternately arranged in such a manner that a pitch between adjacent phase change regions and adhesive regions is 0 mm.

In the present specification, as shown in fig. 6, the Machine Direction (MD) refers to the line direction (flow direction) in the process of manufacturing the composite sheet. Although not particularly limited, when the composite sheet is in the form of a strip having a long length, the MD direction of the composite sheet or the temperature control layer is generally aligned with the longitudinal direction thereof. The Transverse Direction (TD) refers to a direction perpendicular to the machine direction (orthogonal direction).

Fig. 4 schematically illustrates a cross-sectional view in the Transverse Direction (TD) of the temperature control layer of the composite sheet of the present invention. As shown in fig. 4, the temperature control layer 30 includes at least one phase change region 4 and at least one adhesive region 3 arranged in an alternating pattern in a Transverse Direction (TD) perpendicular to the machine direction of the temperature control layer, no gap is present between two adjacent phase change regions 4 and adhesive regions 3, the adjacent phase change regions 4 and adhesive regions 3 are disposed in a closely alternating manner, and edges 41 and 31 of the adjacent phase change regions 4 and adhesive regions 3 are in contact with each other. By alternately arranging the phase change region and the adhesive region, even if the composite sheet has a small thickness, the phase change heat absorption enthalpy value can be favorably increased, the cycle use frequency is increased, and the glue overflow phenomenon can be obviously improved.

Fig. 5 is a cross-sectional view schematically showing a Transverse Direction (TD) of a composite sheet according to an embodiment of the present invention. As shown in fig. 5, the composite sheet 100 includes a temperature control layer 30, a first substrate layer 10 disposed on a first side of the temperature control layer 30, a second substrate layer 20 disposed on a second side of the temperature control layer 30, a backing layer 40 disposed between the temperature control layer 30 and the first substrate layer 10, and a backing layer 50 disposed between the temperature control layer 30 and the second substrate layer 20, wherein the temperature control layer 30 includes at least one phase change region 4 and at least one adhesive region 3 arranged in a close alternating pattern in a Transverse Direction (TD) of the temperature control layer perpendicular to a machine direction, and the phase change region 4 and the adhesive region 3 are alternately disposed such that a distance between adjacent phase change regions and adhesive regions is 0 mm.

The phase change region and the adhesive region are not particularly limited as long as they are formed alternately in a periodic manner. In some preferred embodiments, when the composite sheet is in the form of a tape or a stripe, the phase change region and the adhesive region may be in the form of a tape or a stripe structure formed along a Transverse Direction (TD) of the temperature control layer perpendicular to the machine direction.

In some preferred embodiments, the phase change region may have any desired length according to practical requirements.

In some preferred embodiments, the phase change region may have any desired width according to practical requirements, for example, the phase change region may have a width of 40 to 200mm, preferably 100 to 150 mm. When the temperature control layer includes a plurality of phase change regions, the width of each phase change region may be the same or may be different. Preferably, the width of each phase change region is the same. The width may be measured by a ruler or a quadratic projector.

In some preferred embodiments, the phase change region may have any desired thickness according to practical requirements, for example, the phase change region may have a thickness of 40 to 80 μm, preferably 50 to 70 μm. When the temperature control layer includes a plurality of phase change regions, it is preferable that the thickness of each phase change region is the same. The thickness can be measured by optical microscopy or Scanning Electron Microscopy (SEM).

In some preferred embodiments, the adhesive region may have any desired length, depending on the actual requirements.

In some preferred embodiments, the adhesive area may have any desired width according to practical requirements, for example, the adhesive area may have a width of 2 to 10mm, preferably 2 to 8 mm. When the temperature control layer comprises a plurality of adhesive regions, the width of each adhesive region may be the same or may be different. Preferably, the width of each adhesive region is the same. The width may be measured by a ruler or a quadratic projector.

In some preferred embodiments, the adhesive region may have any desired thickness according to practical requirements, for example, the adhesive region may have a thickness of 40 to 80 μm, preferably 50 to 70 μm. When the temperature control layer comprises a plurality of adhesive regions, it is preferred that each adhesive region has the same thickness. Preferably, the thickness of the adhesive region is the same as the thickness of the phase change region. The thickness can be measured by optical microscopy or SEM.

In some preferred embodiments, the area ratio of the adhesive region to the phase change region is preferably 0:1 to 10:1, more preferably 0.01:1 to 10:1, and even more preferably 0.01:1 to 5: 1. By making the area ratio of the adhesive region to the phase change region fall within the above range, the phase change enthalpy value can be advantageously increased even if the composite sheet has a small thickness, the number of times of recycling can be increased, and the occurrence of the glue overflow phenomenon can be suppressed, so that the workability and the production efficiency can be greatly improved.

The number of phase change regions and adhesive regions is not particularly limited as long as they are periodically and alternately arranged. In some preferred embodiments, the number of the phase change regions is preferably 1 to 30, and the number of the adhesive regions is preferably 1 to 30.

The method for forming the phase change region and the adhesive region in an alternating arrangement is not particularly limited as long as the phase change region and the adhesive region can be periodically and alternately formed in a Transverse Direction (TD) perpendicular to the machine direction of the temperature control layer. From the viewpoint of simplicity, a method of forming the phase change regions and the binder regions alternately arranged by transfer by printing, coating, or the like is preferably employed.

(phase transition region)

The phase change region is formed from a temperature control composition comprising a first binder and a first phase change material.

As the first binder, any suitable binder may be used as long as the effects of the present invention can be obtained. In some preferred embodiments, the first adhesive comprises a hot melt adhesive.

Examples of the material of the hot-melt adhesive include: styrene thermoplastic elastomers, polyvinyl acetate adhesives, olefin resins, acrylic resins, and the like. These materials may be used alone or in combination.

Preferred examples of the styrene-based thermoplastic elastomer include: hydrogenated styrene-butadiene rubber (HSBR), styrenic block copolymers or hydrogenated products thereof, and the like.

Examples of the styrenic block copolymer include: styrenic ABA type block copolymers (triblock copolymers), such as styrene-butadiene-styrene copolymers (SBS) and styrene-isoprene-styrene copolymers (SIS); styrenic ABAB type block copolymers (tetrablock copolymers), such as styrene-butadiene-styrene-butadiene copolymer (SBSB) and styrene-isoprene-styrene-isoprene copolymer (SISI); styrenic ABABABA type block copolymers (pentablock copolymers), such as styrene-butadiene-styrene copolymers (SBSBS) and styrene-isoprene-styrene copolymers (SISIS); and styrenic block copolymers with more AB repeat units, and the like. Among these, styrene-butadiene-styrene copolymer (SBS) is preferable as the styrenic block copolymer in view of better obtaining the effect of the present invention.

Examples of the hydrogenation product of a styrenic block copolymer include: styrene-ethylene-butylene copolymer-styrene copolymer (SEBS), styrene-ethylene-propylene copolymer-styrene copolymer (SEPS), styrene-ethylene-butylene copolymer-styrene-ethylene-butylene copolymer (sebsebseb), and the like.

The material as the first binder may contain any other styrene-based thermoplastic elastomer to the extent that the effects of the present invention are not impaired. Examples of other styrenic thermoplastic elastomers include: a styrenic block copolymer other than the above-mentioned styrenic block copolymer; AB type block copolymers such as styrene-butadiene copolymer (SB), styrene-isoprene copolymer (SI), copolymer of styrene-ethylene-butylene copolymer (SEB), and copolymer of styrene-ethylene-propylene copolymer (SEP); styrenic random copolymers such as styrene-butadiene rubber (SBR); A-B-C type styrene-olefin crystalline block copolymers such as styrene-ethylene-butene copolymer-olefin crystalline copolymer (SEBC); and hydrogenated products thereof. Other styrenic thermoplastic elastomers may be used alone or in combination.

Examples of the polyvinyl acetate-based adhesive include an ethylene-vinyl acetate copolymer (EVA) adhesive and the like. As the ethylene-vinyl acetate copolymer, a known or well-known ethylene-vinyl acetate copolymer can be used.

In the material as the first binder, additives such as a tackifier, a crosslinking agent, a softener, an anti-aging agent, a leveling agent, a plasticizer, an antioxidant, a corrosion inhibitor, a polymerization inhibitor, a silane coupling agent, an inorganic or organic filler (e.g., calcium oxide, magnesium oxide, silica, zinc oxide, or titanium oxide), a heat stabilizer, or the like may be suitably added as needed.

In some preferred embodiments, the first adhesive has a bleed width of 1mm or less, more preferably 0.5mm or less, at 150 ℃x0.1 MPa x 1H. When the glue overflow width of the first adhesive falls into the range under the condition of 150 ℃ multiplied by 0.1MPa multiplied by 1H, the adhesive can be effectively controlled not to overflow to the outside, and the situations of pollution of electronic components and the like are avoided. The bleed width can be measured, for example, by an electron microscope.

In some preferred embodiments, the first adhesive has an adhesive force of 1.0 to 20N/10mm, preferably 3.0 to 20N/10mm, and more preferably 5.0 to 20N/10mm after passing through the adhesive at 85 ℃ and 0.1MPa for 10 seconds. When the adhesive force of the first adhesive after 10 seconds at 85 ℃ and 0.1MPa falls within the above range, the effect of the adhesiveness required in use can be sufficiently exhibited, excellent bonding reliability can be achieved, and the flash phenomenon does not occur.

If the first adhesive has an adhesive strength of less than 1.0N/20mm after 10 seconds at 85 ℃ and 0.1MPa, insufficient adhesion tends to occur, resulting in separation of the temperature-controlling layer from the back sheet or the base material layer. If the adhesive force of the first adhesive is greater than 20N/20mm after the first adhesive passes through 10s at 85 ℃ and 0.1MPa, glue overflow occurs in the high-temperature operation process due to the excessively strong adhesive force, so that electronic components are polluted, and the yield is greatly reduced. The adhesive force can be measured, for example, by the method described in the examples described below.

In some preferred embodiments, the first binder has a density of 1.0g/cm³Hereinafter, more preferably 0.9g/cm³The following. When the density of the first adhesive falls within the above range, an excellent adhesive in which the adhesive force is not reduced upon a temperature change can be provided. The above density can be measured, for example, as follows: the cut piece of the sheet formed of the first binder was subjected to a heat treatment at 85 ℃ for 0.5 hour, slowly cooled to room temperature over 0.5 hour, and then the density was measured by a balance method.

In some preferred embodiments, the first binder has a melt index at a temperature of 230 ℃ under a load of 5kg of 10g/min or less, preferably 5g/min or less. When the melt index of the first adhesive falls within the above range, good shape retention can be exerted. If the first adhesive has a melt index of more than 10g/min, since such a low viscosity polymer tends to flow, flash occurs at the time of high temperature and high pressure operation, contaminating electronic parts, resulting in a decrease in yield. The melt index can be measured, for example, by the method described in examples described later.

In some preferred embodiments, the mass percentage of the first binder in the phase change region is 5 to 25%, preferably 10 to 20%. When the mass percentage of the first adhesive is within the above range, the function of the first adhesive can be sufficiently exhibited, excellent bonding reliability can be achieved, and the flash phenomenon does not occur.

As the first phase change material, an appropriate phase change material may be used as long as the effects of the present invention can be obtained. The term "phase change material" as used herein refers to a material that has the ability to absorb or release heat to regulate heat transfer in or within a temperature stability range. The temperature stability range may include a particular transition temperature or a range of transition temperatures. In some cases, a phase change material may be able to inhibit heat transfer for a period of time as the phase change material absorbs or releases heat, typically as the phase change material undergoes a transition between two states. This action is typically temporary and does not occur until the latent heat of the phase change material is absorbed or released during the heating or cooling process. Heat can be stored or removed from the phase change material, and the phase change material typically can be effectively replenished by a source that emits or absorbs heat. For some embodiments, the phase change material may be a mixture of two or more materials. By selecting two or more different materials and forming a mixture, the temperature stability range can be adjusted for any desired application. The resulting mixture, when introduced into the phase change region described herein, may exhibit two or more different transition temperatures or a single modified transition temperature.

In some preferred embodiments, the first phase change material includes hydrocarbon compounds, fatty acid compounds, alcohol compounds, ester compounds, and the like. These may be used alone or in combination of 2 or more. Among these, the phase change material is preferably a hydrocarbon compound from the viewpoint of effectively improving the heat conductive property and being easily available.

Examples of the hydrocarbon compounds include: an aliphatic hydrocarbon group compound having 8 to 100 carbon atoms (preferably an aliphatic hydrocarbon group compound having 10 to 80 carbon atoms, more preferably an aliphatic hydrocarbon group compound having 15 to 50 carbon atoms, further preferably an aliphatic hydrocarbon group compound having 18 to 30 carbon atoms), an aromatic hydrocarbon group compound having 6 to 120 carbon atoms (preferably an aromatic hydrocarbon group compound having 8 to 100 carbon atoms, more preferably an aromatic hydrocarbon group compound having 10 to 50 carbon atoms, further preferably an aromatic hydrocarbon group compound having 12 to 30 carbon atoms), an alicyclic hydrocarbon group compound having 6 to 100 carbon atoms (preferably an alicyclic hydrocarbon group compound having 6 to 80 carbon atoms, more preferably an alicyclic hydrocarbon group compound having 6 to 50 carbon atoms, further preferably an alicyclic hydrocarbon group compound having 6 to 30 carbon atoms), a method for producing the same, and a method for producing the same, Paraffin (melting point 5-80 ℃ C.), and the like.

The aliphatic hydrocarbon-based compound having 8 to 100 carbon atoms may be a linear or branched aliphatic hydrocarbon-based compound, and examples thereof include, but are not limited to, n-octadecane, n-nonadecane, n-eicosane, n-heneicosane, n-docosane, n-tetracosane, n-pentacosane, n-hexacosane, n-heptacosane, n-octacosane, and the like.

Examples of the aromatic hydrocarbon-based compound having 6 to 120 carbon atoms include, but are not limited to, benzene, naphthalene, biphenyl, ortho-terphenyl, n-terphenyl, and the like. In some embodiments, the aromatic hydrocarbyl compound having 6 to 120 carbon atoms may be a substituted aromatic hydrocarbyl compound having 6 to 100 carbon atoms, preferably C₁-C₄₀An alkyl-substituted aromatic hydrocarbon-based compound having 6 to 100 carbon atoms. C₁-C₄₀Examples of alkyl-substituted aromatic hydrocarbyl compounds include, but are not limited to, dodecylbenzene, tetradecylbenzene, hexadecylbenzene, hexylnaphthalene, decylnaphthalene, and the like.

Examples of the alicyclic hydrocarbon compound having 6 to 100 carbon atoms include, but are not limited to, cyclohexane, cyclooctane, cyclodecane and the like.

The fatty acid-series compound is preferably a saturated or unsaturated C₆-C₃₀Fatty acids, examples of which include, but are not limited to, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and the like. These may be used alone or in combination of 2 or more.

As the alcohol compound, C is preferred₃-C₂₀Fatty alcohols, examples of which include, but are not limited to, glycerol, erythritol, dodecanol, tetradecanol, hexadecanol, erythritolStearyl alcohol, oleyl alcohol, mixtures such as coconut fatty alcohol, and so-called oxo alcohols obtained by hydroformylating alpha-olefins and further reacting, and the like. These may be used alone or in combination of 2 or more.

As the ester compound, C of a fatty acid is preferred₁-C₃₀Alkyl esters, examples of which include, but are not limited to, cetyl stearate, cellulose laurate, propyl palmitate, methyl stearate, methyl palmitate, and the like. These may be used alone or in combination of 2 or more.

In some preferred embodiments, the first phase change material comprises graft-modified phase change energy storage particles. The graft-modified phase-change energy storage particles are obtained by graft modification of an unmodified phase-change material.

As the unmodified phase change material, for example, the above-mentioned hydrocarbon compound, fatty acid compound, alcohol compound, ester compound, and the like can be used.

Examples of the modifier include unsaturated carboxylic acids. Specifically, examples thereof include: unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid, and derivatives of these unsaturated carboxylic acids, for example, unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic acid imides, and ester compounds of unsaturated carboxylic acids. Examples of the derivative of the unsaturated carboxylic acid include maleic anhydride, citraconic anhydride, maleic acid chloride, maleimide, monomethyl maleate, dimethyl maleate, and glycidyl maleate. These modifiers may be used alone, or 2 or more kinds may be used in combination.

The method of graft modification is not particularly limited, and may be carried out by a method known to those skilled in the art. For example, it can be carried out by polymerization.

In some preferred embodiments, it is preferable to use, for example, azobisisobutyronitrile or the like as a polymerization initiator at the time of graft modification.

The amount of the polymerization initiator is 0.02 to 5 parts by weight relative to 100 parts by weight of the unmodified phase change material. When the amount of the polymerization initiator is too small, the graft polymerization reaction takes too much time, and when the amount of the polymerization initiator is too large, the homopolymer increases, which is not preferable.

The obtained graft modification phase change energy storage particles have the advantages of high energy storage density, high energy conversion efficiency, good stability and the like, and when the graft modification phase change energy storage particles are used in the temperature control layer, a high phase change heat absorption enthalpy value can be obtained even if the thickness of the composite sheet is thin, so that the recycling times of the composite sheet are greatly improved.

In some preferred embodiments, the phase transition temperature of the graft modified phase change energy storage particles is 30 to 50 ℃, preferably 35 to 45 ℃. When the phase change temperature of the graft modified phase change energy storage particles falls within the range, the function of the graft modified phase change energy storage particles can be fully exerted, and the effect of high phase change heat absorption enthalpy value is realized. If the phase change temperature of the graft modified phase change energy storage particles is lower than 30 ℃, more phase change energy storage particles need to be added to achieve the effect of high phase change heat absorption enthalpy value, so that the bonding force between the temperature control layer and the bottom lining layer or the base material layer is reduced, and the use times are reduced. If the phase change temperature of the graft modification phase change energy storage particles is higher than 50 ℃, the temperature reduction range of the system after the temperature control layer absorbs heat is small, so that a large amount of heat still exists in the system, heat accumulation occurs again, and the reject ratio is increased.

In some preferred embodiments, the particle size distribution of the graft-modified phase-change energy storage particles is 2 to 100 μm, preferably 20 to 40 μm. When the particle size distribution of the graft modified phase change energy storage particles falls within the range, the function of the graft modified phase change energy storage particles can be fully exerted, and the effect of high phase change heat absorption enthalpy value is realized under the condition that the overall thickness of the composite sheet is relatively thin.

In some preferred embodiments, the content of the graft-modified phase change energy storage particles having a particle size distribution of 10 μm or less in the entire graft-modified phase change energy storage particles is 10% by volume or less, preferably 5% by volume or less. The effect of the invention can be better realized by controlling the proportion of the graft modified phase-change energy storage particles with the particle size distribution of less than 10 mu m, and the high phase-change heat absorption enthalpy value is obtained. When the content of the graft modified phase change energy storage particles with the particle size distribution of less than 10 mu m is more than 10 volume percent, the overall heat absorption enthalpy value is reduced, more phase change energy storage particles are required to be added for achieving the purpose of high heat absorption enthalpy value, and further the bonding force between the temperature control layer and the bottom lining layer or the base material layer is reduced, and the use times are reduced.

In some preferred embodiments, the graft-modified phase change energy storage particles have an enthalpy of phase change of 190J/g or more. When the phase change enthalpy value of the graft modified phase change energy storage particles falls within the range, the high phase change heat absorption enthalpy value can be better obtained.

In some preferred embodiments, the mass percentage of the graft modified phase change energy storage particles in the phase change region is 75-95%, preferably 80-90%. By enabling the mass percentage of the graft modified phase-change energy storage particles to be in the range, the function of the graft modified phase-change energy storage particles can be fully exerted, and the effect of high phase-change heat absorption enthalpy value is realized. When the mass percentage is less than 75%, the conversion efficiency of energy is low, which is not favorable for obtaining the effect of the present invention. When the mass percentage of the phase-change energy storage particles is more than 95%, the addition amount of the phase-change energy storage particles is large, so that the bonding force between the temperature control layer and the bottom lining layer or the base material layer is reduced, the damage is easy to occur, the use times are reduced, and the composite sheet is easy to overflow glue to pollute electronic components at high temperature and high pressure.

The temperature control composition of the present invention may contain, in addition to the above-mentioned components, various additives such as a crosslinking agent, a tackifier, a leveling agent, a crosslinking aid, a plasticizer, a softening agent, an antistatic agent, an antioxidant, and the like as needed within a range not to impair the effects of the present invention. With respect to such various additives, conventionally known additives can be used by a conventional method.

(adhesive region)

The adhesive region is formed from an adhesive composition comprising a second adhesive.

The second adhesive may be the same as or different from the first adhesive. In some preferred embodiments, the second adhesive comprises a hot melt adhesive. As the hot melt adhesive, the hot melt adhesive explained in the above-mentioned first adhesive is preferably used, and will not be described in detail here.

In some preferred embodiments, the second adhesive has a bleed width of 1mm or less, more preferably 0.5mm or less, at 150 ℃x0.1 MPa x 1H. When the glue overflow width of the second adhesive is in the range under the conditions of 150 ℃ multiplied by 0.1MPa multiplied by 1H, the adhesive can be effectively controlled not to overflow to the outside, and the occurrence of poor operation is avoided.

In some preferred embodiments, the second adhesive has an adhesive force of 1.0 to 20N/10mm, preferably 3.0 to 20N/10mm, and more preferably 5.0 to 20N/10mm after passing at 85 ℃ and 0.1MPa for 10 seconds. When the adhesive force of the second adhesive after 10 seconds at 85 ℃ and 0.1MPa falls within the above range, the effect of the adhesiveness required in use can be sufficiently exhibited, excellent bonding reliability can be achieved, and the flash phenomenon does not occur.

If the second adhesive has an adhesive force of less than 1.0N/20mm after 10 seconds at 85 ℃ and 0.1MPa, insufficient adhesion tends to occur, resulting in separation of the temperature-controlling layer from the back sheet or the base material layer. If the adhesive force of the second adhesive is greater than 20N/20mm after passing through the second adhesive for 10s at 85 ℃ and 0.1MPa, glue overflow occurs in the high-temperature operation process due to the excessively strong adhesive force, so that electronic components are polluted, and the yield is greatly reduced.

In some preferred embodiments, the second binder has a density of 1.0g/cm³Hereinafter, more preferably 0.9g/cm³The following. When the density of the second adhesive falls within the above range, an excellent adhesive in which the adhesive force is not reduced upon a temperature change can be provided.

In some preferred embodiments, the second binder has a melt index at a temperature of 230 ℃ under a load of 5kg of 10g/min or less, preferably 5g/min or less. When the melt index of the second adhesive falls within the above range, good shape retention can be exerted. If the second adhesive has a melt index of more than 10g/min, since such a low viscosity polymer tends to flow, flash occurs at the time of high temperature and high pressure operation, contaminating electronic parts, resulting in a decrease in yield.

In some preferred embodiments, the second binder is present in the binder region in an amount of 80 to 100% by mass, preferably 85 to 95% by mass. By making the mass percentage of the second adhesive within the above range, excellent bonding reliability can be achieved, and the flash phenomenon does not occur.

In some preferred embodiments, the adhesive region comprises a second phase change material.

The second phase change material may be the same as or different from the first phase change material. In some preferred embodiments, the second phase change material comprises graft-modified phase change energy storage particles. As the graft-modified phase change energy storage particles, the graft-modified phase change energy storage particles explained in the above-mentioned first phase change material are preferably used, and will not be described in detail here.

In some preferred embodiments, the content of the second phase change material in the adhesive region is 0 to 20 mass%, preferably 5 to 15 mass%.

In some preferred embodiments, the thickness of the temperature control layer is 40 to 80 μm, preferably 50 to 70 μm. By making the thickness of the temperature control layer fall within the above range, the composite sheet can advantageously increase the phase change heat absorption enthalpy value, increase the number of cycles, and suppress the occurrence of the flash phenomenon even when the composite sheet has a small thickness.

In some preferred embodiments, the interlayer strength of the temperature control layer is 1.0 to 20.0N/10mm, preferably 3.0 to 20.0N/10 mm. When the interlayer strength of the temperature-controlled layer falls within the above range, the cohesive strength of the temperature-controlled layer is excellent, and the cohesive strength and the processability can be taken into consideration at a higher level. If the interlayer strength of the temperature control layer is less than 1.0N/10mm, the cohesive strength is weak, and the interlayer fracture and other disadvantages are likely to occur in the aspect of durability. If the interlayer strength of the temperature control layer is more than 20.0N/10mm, the cohesive strength is too strong, so that the adhesive force of the temperature control layer is reduced, the bonding force between the temperature control layer and the bottom lining layer or the base material layer is reduced, anchoring damage is easy to occur in the using process, the pollution to electronic components is caused, and the yield is greatly reduced.

In some preferred embodiments, the length and width of the temperature control layer can be the same or different from the length and width of the composite sheet, preferably the length and width of the temperature control layer is the same as the length and width of the composite sheet.

[ first base material layer ]

The material constituting the first base material layer disclosed herein is not particularly limited, and may be appropriately selected depending on the purpose of use, the mode of use, and the like of the composite sheet. Examples of the usable first substrate layer include, but are not limited to, plastic films such as polyolefin films mainly composed of polyolefins such as polypropylene and ethylene-propylene copolymers, polyester films mainly composed of polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polyvinyl chloride films mainly composed of polyvinyl chloride; foam sheets formed of foams such as polyurethane foam, polyethylene foam, and polychloroprene foam; woven and nonwoven fabrics obtained from various fibrous materials (natural fibers such as hemp and cotton, synthetic fibers such as polyester and vinylon, and semisynthetic fibers such as acetate fibers, etc.) alone or by blending; papers such as japanese paper, high-quality paper, kraft paper, crepe paper, and the like; metal foils such as aluminum foil and copper foil. The substrate may be a composite structure of these materials.

As the first base material layer disclosed herein, various film base materials can be preferably used. As the film substrate, a film substrate including a resin film capable of independently maintaining a shape (a free-standing type or an independent type) as a base film can be preferably used. The term "resin film" as used herein means a resin film which has a non-porous structure and is typically substantially free of air bubbles (void-free). Therefore, the resin film is a concept different from a foamed film and a nonwoven fabric. The resin film may have a single-layer structure or a multilayer structure (for example, a three-layer structure) having two or more layers.

Examples of the resin material constituting the resin film include a Polyamide (PA) such as polyester, polyolefin, nylon 6, nylon 66, and partially aromatic polyamide, a Polyimide (PI), polyamide imide (PAI), polyether ether ketone (PEEK), polyether sulfone (PES), polyphenylene sulfide (PPS), Polycarbonate (PC), Polyurethane (PU), ethylene-vinyl acetate copolymer (EVA), a fluororesin such as Polytetrafluoroethylene (PTFE), an acrylic resin, a polyacrylate, polystyrene, polyvinyl chloride, and polyvinylidene chloride. The resin film may be formed using a resin material containing one kind of such resin alone, or may be formed using a resin material in which two or more kinds of resins are mixed. The resin film may be unstretched or stretched (for example, uniaxially stretched or biaxially stretched).

Suitable examples of the resin material constituting the resin film include a polyester resin, a PPS resin, and a polyolefin resin. The polyester resin is a resin containing a polyester in a proportion of more than 50% by weight. Similarly, the PPS resin refers to a resin containing PPS in a proportion of more than 50 wt%, and the polyolefin resin refers to a resin containing polyolefin in a proportion of more than 50 wt%.

As the polyester resin, typically, a polyester resin containing as a main component a polyester obtained by polycondensing a dicarboxylic acid and a diol is used. Specific examples of the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polybutylene naphthalate.

As the polyolefin resin, one kind of polyolefin may be used alone, or two or more kinds of polyolefins may be used in combination. The polyolefin may be, for example, a homopolymer of an α -olefin, a copolymer of two or more α -olefins, a copolymer of one or two or more α -olefins with another vinyl monomer, or the like. Specific examples thereof include ethylene-propylene copolymers such as Polyethylene (PE), polypropylene (PP), poly-1-butene, poly-4-methyl-1-pentene and Ethylene Propylene Rubber (EPR), ethylene-propylene-butene copolymers, ethylene-vinyl alcohol copolymers and ethylene-ethyl acrylate copolymers. Any of Low Density (LD) polyolefin and High Density (HD) polyolefin may be used. Examples of the polyolefin resin film include a non-stretched polypropylene (CPP) film, a biaxially stretched polypropylene (OPP) film, a Low Density Polyethylene (LDPE) film, a Linear Low Density Polyethylene (LLDPE) film, a Medium Density Polyethylene (MDPE) film, a High Density Polyethylene (HDPE) film, a Polyethylene (PE) film in which two or more kinds of Polyethylenes (PE) are mixed, and a PP/PE mixed film in which polypropylene (PP) and Polyethylene (PE) are mixed.

Specific examples of the resin film that can be preferably used as the base film of the composite sheet disclosed herein include a PET film, a PEN film, a PPS film, a PEEK film, a CPP film, and an OPP film. Examples of the base film preferable from the viewpoint of strength and dimensional stability include a PET film, a PEN film, a PPS film, and a PEEK film.

The resin film may contain known additives such as an antioxidant, a filler, and an antiblocking agent as needed within a range not significantly impairing the effects of the present invention. The amount of the additive to be blended is not particularly limited, and may be appropriately set according to the use of the composite sheet and the like.

The method for producing the resin film is not particularly limited. For example, conventionally known common resin film forming methods such as extrusion molding, blow molding, T-die casting molding, calender roll molding, and the like can be suitably used.

The surface of the first base material layer may be subjected to conventionally known surface treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and the like, as necessary. Such a surface treatment may be a treatment for improving the anchorage of the temperature control layer to the first substrate layer.

The thickness of the first substrate layer is preferably 2 to 12 μm, and more preferably 2 to 6 μm. When the thickness of the first base material layer falls within the above range, the effects of the present invention can be further exhibited, and workability and handleability can be further improved.

In some preferred embodiments, the length and width of the first substrate layer may be greater than or the same as the length and width of the composite sheet, preferably the same as the length and width of the composite sheet.

In some preferred embodiments, the density of the first substrate layer is 1.4g/cm³Hereinafter, it is preferably 1.0g/cm³The following. When the density of the first substrate layer falls within the range, the unit phase change heat absorption enthalpy value of the composite sheet can be improved, and the weight of the composite sheet is reduced. The density can be measured, for example, by a density tester.

In some preferred embodiments, the first substrate layer has a thermal conductivity of 0.15 to 0.6W/M.K, preferably 0.3 to 0.6W/M.K. When the heat conduction coefficient of the first base material layer falls within the above range, an excellent heat conduction effect can be provided, and workability and handleability are improved. The thermal conductivity can be measured, for example, by a thermal conductivity meter.

In some preferred embodiments, the anchoring force between the temperature control layer and the first substrate layer is 1.0-20.0N/10 mm, preferably 3.0-20.0N/10 mm. When the anchoring force falls within the above range, the adhesion between the temperature-control layer and the first base material layer is excellent, and the adhesion and the workability can be achieved at a higher level. If the anchoring force between the temperature control layer and the first base material layer is less than 1.0N/10mm, the adhesion is weak, and defects such as peeling easily occur in terms of durability. If the anchoring force between the temperature control layer and the first base material layer is larger than 20N/10mm, glue overflow occurs in the high-temperature operation process due to the fact that the adhesive force is too strong, electrode pollution is caused, and the yield is greatly reduced. The anchoring force can be measured, for example, by the method described in the examples described below.

[ second base material layer ]

The material of the second base material layer may be the same as or different from the material of the first base material layer. In some preferred embodiments, the substrate layer described in the above-described first substrate layer is preferably used as the second substrate layer, and will not be described in detail herein.

In some preferred embodiments, the thickness of the second substrate layer is preferably 2 to 12 μm, and more preferably 2 to 6 μm. When the thickness of the second base material layer falls within the above range, the effects of the present invention can be further exhibited, and workability and handleability can be further improved.

In some preferred embodiments, the length and width of the second substrate layer may be greater than or the same as the length and width of the composite sheet, preferably the same as the length and width of the composite sheet.

In some preferred embodiments, the density of the second substrate layer is 1.4g/cm³Hereinafter, it is preferably 1.0g/cm³The following. When the density of the second substrate layer falls within the range, the unit phase change heat absorption enthalpy value of the composite sheet can be improved, and the weight of the composite sheet is reduced.

In some preferred embodiments, the second substrate layer has a thermal conductivity of 0.15 to 0.6W/M.K, preferably 0.3 to 0.6W/M.K. When the heat conduction coefficient of the second base material layer falls within the above range, an excellent heat conduction effect can be provided, and workability and handleability are improved.

In some preferred embodiments, the anchoring force between the temperature control layer and the second substrate layer is 1.0-20N/10 mm, preferably 3.0-20.0N/10 mm. When the anchoring force falls within the above range, the adhesion between the temperature-control layer and the second base material layer is excellent, and the adhesion and the workability can be achieved at a higher level. If the anchoring force between the temperature control layer and the second base material layer is less than 1.0N/10mm, the adhesion is weak, and defects such as peeling easily occur in terms of durability. If the anchoring force between the temperature control layer and the second substrate layer is larger than 20N/10mm, glue overflow occurs in the high-temperature operation process due to the fact that the adhesive force is too strong, electrode pollution is caused, and the yield is greatly reduced.

[ underlayment ]

The bottom lining layer is arranged between the temperature control layer and the first base material layer and/or between the temperature control layer and the second base material layer.

The underlayer may have a conventionally known structure, and is not particularly limited, and examples thereof include: urethane (polyisocyanate) resins, polyester resins, acrylic resins, polyamide resins, melamine resins, olefin resins, polystyrene resins, epoxy resins, phenol resins, isocyanurate resins, and polyvinyl acetate resins.

In some preferred embodiments, the resin used for the undercoat layer may be a resin that has reactivity such as crosslinking curing, polymerization, condensation, and the like, and exhibits the physical properties by reacting the resin. A crosslinking agent may be added as appropriate during crosslinking and curing. In addition, other functional additives may be added to the backing layer to impart other functions.

The undercoat layer can be formed by a method of pressure-bonding a thin film made of the above-exemplified material for forming the undercoat layer to a plastic base, a method of applying a molten material of the material for forming and cooling, or a method of applying a solution of the material for forming and drying. The coating method may be appropriately selected, and gravure coating, reverse roll coating, spray coating, or the like may be preferably used.

The backing layer may have any one of a single layer and a multilayer structure. The thickness of the undercoat layer can be selected from the range of 1 to 5 μm, preferably 1 to 3 μm. When the thickness of the bottom liner layer is too thin, the thickness becomes uneven, and the anchoring force of the base material layer and the temperature control layer is reduced, and on the other hand, the processing adaptability may be poor.

In some preferred embodiments, the length and width of the backing layer may be greater than or the same as the length and width of the composite sheet, preferably the same as the length and width of the composite sheet.

(method of producing composite sheet)

The composite sheet of the present invention may be manufactured by any suitable method. Examples of the method include the following: and coating a bottom lining layer or a temperature control layer on the first substrate layer, and synchronously laminating the second substrate layer.

As a method of coating the temperature control composition or the adhesive composition, any suitable coating method may be employed. For example, each layer may be formed by drying after coating. Examples of the coating method include coating methods using a die coater, a gravure coater, an applicator, a bar coater, air knife coating, reverse roll coating, lip coating, dip coating, offset printing, flexographic printing, screen printing, and the like. Examples of the drying method include natural drying and heat drying. The heating temperature in the case of heat drying may be set to any appropriate temperature depending on the characteristics of the substance to be dried.

< use >

The composite sheet disclosed herein can be embedded in various electronic components (for example, a battery, particularly a nonaqueous battery such as a lithium ion battery) and is preferably used for applications such as isolation, temperature control, and protection of the components.

Examples

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The evaluation methods in the examples are as follows. In the examples, "part(s)" and "%" are based on weight unless otherwise specified.

< evaluation test >

(1) Enthalpy value of phase change heat absorption

The composite sheets obtained in the above examples and comparative examples were subjected to a 20 ℃ to 100 ℃ (at a temperature rise rate of 10 ℃/min) test using DSC (differential scanning calorimeter), and the enthalpy value of the phase transition endotherm was confirmed. The results are shown in tables 1 and 2.

(2) Adhesive force

The adhesive sheets formed from the first adhesive or the second adhesive of each example and each comparative example were cut to have a width of 20mm × a length of 150mm to prepare test pieces. A SUS plate (SUS430BA plate) cleaned with toluene was used as an adherend.

The release liner covering the adhesive surface of each test piece was peeled off under a standard environment of 23 ℃ and 50% RH, and a 2kg roller was reciprocated 1 time to pressure bond the exposed adhesive surface to the adherend. The test piece pressure-bonded to the adherend was heated at 85 ℃ for 10 seconds under 0.1MPa, and then left to stand under the above-mentioned standard environment for 30 minutes, and then subjected to a tensile test using a tensile tester (trade name "Shimadzu Autograph AG-120 kN" manufactured by Shimadzu Corporation) according to JIS Z0237 at a tensile rate: 300 mm/min, peel angle: peeling was performed at 180 ℃ and the force required for the peeling (180 ℃ peel adhesion) (N/20mm) was measured. The results are shown in tables 1 and 2.

(3) Melt index

Using a melt index instrument (model name "

CEAST MF50 ", manufactured by Instron, usa), according to JIS K7210: 1999 or ASTM D1238, the melt index of the first adhesive and the second adhesive was measured under the condition of temperature 230 ℃ and load 5 kg.

(4) Anchoring force

A polyester adhesive tape (trade name "No. 315# 25", manufactured by hitto electric Corporation) having a width of 19mm was pressure-bonded to the first base material layer (or the second base material layer) of the composite sheet by reciprocating a 2kg roller 1 time at 23 ℃ under a standard environment of 50% RH, and left at 25 ℃ for 30 minutes or more, and then a peel stress at a peel angle of 180 ° at a speed of 300 mm/minute was measured using a tensile tester (trade name "Shimadzu Autograph AG-120 kN", manufactured by Shimadzu Corporation) to obtain an anchoring force between the temperature control layer and the first base material layer (or the second base material layer).

(5) Reusability

The composite sheets (100mm × 200mm) obtained in the above examples and comparative examples were manually bent in a reciprocating manner several times, cut along the bending position with scissors, and checked for delamination, and the resulting composite sheets were subjected to repeated cycles of 20 ℃ to 100 ℃ (at a temperature rise rate of 10 ℃/min) using a DSC (differential scanning calorimeter) to measure the phase change endothermic enthalpy, and the number of times the phase change endothermic enthalpy is reduced to less than 95g/J (that is, 95g/J is not included) by the delamination or the phase change endothermic enthalpy was determined as the reusability. Evaluation was carried out according to the following criteria.

Very good: no layering and reuse times of more than 50

O: no layering, and reuse times of 30-50 times

X: layering occurs, and the number of repeated use is less than 30

(6) Resistance to flash

The composite sheets (10 mm. times.200 mm) obtained in the above examples and comparative examples were placed between two transparent PET #50 substrates at intervals, and the whole was placed between an upper die set and a lower die set of a hot press laminator, heated at 85 ℃ under 0.1MPa for 2 hours, and then the adhesive overflow distance on both sides of the composite sheet was observed under an electron microscope. Evaluation was carried out according to the following criteria.

Very good: the glue overflow distance L is less than or equal to 0.5mm

O: the glue overflow distance L is more than 0.5mm and less than or equal to 1.0mm

X: the glue overflow distance L is more than 1.0mm

(7) Interlaminar strength

The composite sheets obtained in the above examples and comparative examples were cut in the MD direction to a dimension of 10mm (td) in width by 200Mm (MD) in length under a standard atmosphere of 23 ℃ and 50% RH to prepare test pieces. One end portion of the test piece in the MD direction was peeled off by about 30mm from the end portion so as to cause interlaminar fracture. Then, the peeled end portion was sandwiched by a chuck of a tensile tester (trade name "Shimadzu Autograph AG-120 kN", manufactured by Shimadzu Corporation) under a standard environment of 23 ℃ and 50% RH, peeled at a tensile rate of 180 ℃ and 300 mm/min, and the peel strength (N/20mm) was measured as the interlayer strength of the temperature control layer of the composite sheet.

Example 1

Into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube and a reflux condenser, 35 parts by weight of acrylic acid, 900 parts by weight of butyl acrylate and 60 parts by weight of vinyl acetate were charged, and stirred for 2 hours while introducing nitrogen. In this manner, oxygen in the polymerization system was removed, and then 3 parts by weight of 2, 2' -Azobisisobutyronitrile (AIBN) as a polymerization initiator was added to conduct polymerization at 60 ℃ for 6 hours under nitrogen substitution to obtain a solution of an acrylic polymer. The weight average molecular weight of the acrylic polymer was 60 ten thousand, and the solid content was 50%.

To the acrylic polymer solution, 2 parts by weight of a trifunctional isocyanate-based compound (trade name "CORONATEL", manufactured by japan polyurethane corporation) was added per 100 parts by weight of the acrylic polymer contained in the solution, and the mixture was stirred and mixed to prepare an acrylic pressure sensitive adhesive a having a gel fraction of 85%.

The whole width of the coating die of the coating machine is used as a first substrate layer, and the density of the whole width of the coating die is 1.35g/cm³PET #6 (trade name: PET FILM (#6), manufactured by DuPont, Fushan) having a thermal conductivity of 0.43W/M.KManufacturing, thickness: 6 μm) to form a first substrate layer having a thickness of 1 μm, and then a PET #23 protective release film (manufactured by Cassiaceae) was laminated on the surface of the first substrate layer to be wound up for use.

Then, a coating die having uniform ribs at intervals was used to coat a temperature control composition prepared as described below on an engineering release film PET #23 (manufactured by cisseliaceae) to form a phase transition region of a temperature control layer having a thickness of 70 μm, and simultaneously, a peeling surface of the first base liner layer (a surface of the first base liner layer from which the PET #23 protects the release film) was laminated. Wherein, the temperature control composition is prepared as follows: SBS (trade name: D1153E, manufactured by kraton) was dissolved with toluene to a binder having a solid content of 20% (melt index of binder 5g/min), and then maleic anhydride-modified alkane (trade name: MPCM 37D, manufactured by microtek laboratories, inc.) and paraffin wax (polyethylene wax, manufactured by jingzhou gold rubber plastic) in an amount of 90% by mass of the total temperature control composition were mixed at a ratio of 7: 3, adding the phase change energy storage particles into the SBS adhesive, and uniformly dispersing the phase change energy storage particles by using a stirrer to obtain the temperature control composition. The particle size distribution of the formed phase change energy storage particles is 10-60 mu m, and the content of the graft modified phase change energy storage particles with the particle size distribution of less than 10 mu m in all the graft modified phase change energy storage particles is 5 vol%.

Next, an adhesive composition prepared as described below was coated on an engineering release film PET #23 (manufactured by cisselike), using a mold having spaced ribs, to form an adhesive region of a temperature control layer having a thickness of 70 μm, and filling space positions were simultaneously compounded with phase transition regions of the previously compounded temperature control layer. Wherein the adhesive composition is prepared as follows: SBS (trade name: D1153E, manufactured by Keteng) was dissolved with toluene to give an adhesive having a solid content of 20% to obtain an adhesive composition.

Then, the whole width of the coating die of the coater was used to form a second substrate layer having a density of 1.35g/cm³The acrylic pressure-sensitive adhesive A was coated on PET #6 (trade name: PET FILM (#6), manufactured by Fushan DuPont, thickness: 6 μ M) having a thermal conductivity of 0.43W/M.K to form a second substrate layer having a thickness of 1 μ M. Finally, the temperature control layer completed before the second bottom lining layer is synchronously compounded to obtain a compoundAnd (6) laminating.

In this example, the phase change regions and the adhesive regions were arranged in an alternating arrangement in the TD direction of the temperature control layer perpendicular to the machine direction of the composite sheet, and the area ratio of the adhesive regions to the phase change regions was 3: 1. The evaluation results are shown in table 1.

Example 2

The whole width of the coating die of the coating machine is used as a first substrate layer, and the density of the whole width of the coating die is 1.35g/cm³The acrylic pressure-sensitive adhesive A prepared in example 1 was applied to PET #6 (product No. PET FILM (#6), manufactured by DuPont, Fushan, thickness: 6 μ M) having a thermal conductivity of 0.43W/M.K to form a first substrate layer having a thickness of 1 μ M, and then a PET #23 protective release FILM (manufactured by Jiangxi Sico.) was laminated on the surface of the first substrate layer and wound up for use.

Then, the temperature control composition prepared in example 1 above was coated on an engineering release film PET #23 (manufactured by cisselike, jiang) using a coating die having uniform spaced ribs to form a phase transition region of the temperature control layer having a thickness of 71 μm, and simultaneously, a peeling surface of the composite first substrate layer (a surface of the release film protected by the peeling PET #23 of the first substrate layer) was performed.

Next, the adhesive composition prepared in the above example 1 was coated on an engineering release film PET #23 (manufactured by cisselike) using a mold having spaced ribs to form adhesive regions of a temperature-controlled layer having a thickness of 71 μm, and filling space positions were simultaneously compounded with phase change regions of the previously compounded temperature-controlled layer.

Then, the density of the second substrate layer was adjusted to 1.35g/cm³And a temperature control layer formed by synchronously compounding PET #6 (trade name: PET FILM (#6), manufactured by Fushan DuPont, thickness: 6 μ M) with a thermal conductivity of 0.43W/M.K.

Example 3

A composite sheet was obtained in the same manner as in example 1, except that the thicknesses of the first substrate layer and the second substrate, the thickness of the phase change region of the temperature-controlling layer, and the thickness of the adhesive region were changed as shown in table 1. The evaluation results are shown in table 1.

Example 4

The whole width of the coating die of the coating machine is used as a first substrate layer, and the density of the whole width of the coating die is 0.8g/cm³PA66 (product number: BONYL-F, 6 μ M thick, manufactured by NONY Japan) having a heat conductivity of 0.54W/M.K was coated with a hot-melt pressure-sensitive adhesive B (product name:

3520, manufactured by roly) to form a first substrate layer having a thickness of 1 μm, and then a PET #23 protective release film (manufactured by cisseliaceae) was attached to the surface of the first substrate layer and wound up for use.

Then, the temperature control composition prepared in example 1 above was coated on an engineering release film PET #23 (manufactured by cisselike, jiang) using a coating die having uniform spaced ribs to form a phase transition region of the temperature control layer having a thickness of 70 μm, and simultaneously, a peeling surface of the composite first substrate layer (a surface of the release film protected by the peeling PET #23 of the first substrate layer) was performed.

Next, the adhesive composition prepared in the above example 1 was coated on an engineering release film PET #23 (manufactured by cisselike) using a mold having spaced ribs to form adhesive regions of a temperature control layer having a thickness of 70 μm, and filling space positions were simultaneously compounded with phase change regions of the previously compounded temperature control layer.

Then, the whole width of the coating die of the coater was used to form a second substrate layer having a density of 0.8g/cm³The acrylic pressure-sensitive adhesive A prepared in example 1 was coated on PA66 (product number: BONYL-F, 6 μ M thick, manufactured by NONY Japan) having a thermal conductivity of 0.54W/M.K to form a second backing layer having a thickness of 1 μ M. And finally, synchronously compounding the second bottom lining layer with the temperature control layer which is finished before the second bottom lining layer is compounded, so as to obtain the composite sheet.

Example 5

In addition to changing the composition of the secondary backing layer as shown in Table 1, that is, using the full width coating die of the coater, the density as the secondary base material layer was 1.35g/cm³PET #6 (trade name: PET FILM (#6) having a thermal conductivity of 0.43W/M.K, manufactured by Fushan DuPont, thickness: 6 μ M) was coated with a hot-melt pressure-sensitive adhesive B (trade name:

3520, manufactured by rison) to form a second substrate layer having a thickness of 1 μm, a composite sheet was obtained in the same manner as in example 1. The evaluation results are shown in table 1.

In this example, the phase change regions and the adhesive regions were arranged in an alternating manner in the TD direction of the temperature control layer perpendicular to the machine direction of the composite sheet, and the area ratio of the adhesive regions to the phase change regions was 9: 1. The evaluation results are shown in table 1.

Example 6

A composite sheet was obtained in the same manner as in example 1, except that the melt index of the first adhesive was changed as shown in table 1, that is, the melt index of the first adhesive was 10 g/min. The evaluation results are shown in table 1.

In this embodiment, the phase change regions and the adhesive regions are arranged in an alternating arrangement in the TD direction of the temperature control layer perpendicular to the machine direction, and the area ratio of the adhesive regions to the phase change regions is 3: 1. The evaluation results are shown in table 1.

Example 7

The whole width of the coating die of the coating machine is used as a first substrate layer, and the density of the whole width of the coating die is 1.35g/cm³PET #6 (trade name: PET FILM (#6) having a thermal conductivity of 0.43W/M.K, manufactured by Fushan DuPont, thickness: 6 μ M) was coated with a hot-melt pressure-sensitive adhesive B (trade name:

3520, manufactured by Raynaud) was formed into a first substrate layer having a thickness of 1 μm, and then PET #23 protective film was attached to the surface of the first substrate layerThe molded film (made by Sijike, Jiangxi) was rolled up for use.

Next, an adhesive composition prepared as described below was coated on an engineering release film PET #23 (manufactured by cisselike), using a mold having spaced ribs, to form an adhesive region of a temperature control layer having a thickness of 70 μm, and filling space positions were simultaneously compounded with phase transition regions of the previously compounded temperature control layer. Wherein the adhesive composition is prepared as follows: EVA (trade name: 260A, manufactured by DuPont) was dissolved in toluene to obtain an adhesive composition having a solid content of 20%.

Then, the whole width of the coating die of the coater was used to form a second substrate layer having a density of 1.35g/cm³PET #6 (trade name: PET FILM (#6) having a thermal conductivity of 0.43W/M.K, manufactured by Fushan DuPont, thickness: 6 μ M) was coated with a hot-melt pressure-sensitive adhesive B (trade name:

3520, manufactured by rhodanea), a second substrate layer was formed with a thickness of 1 μm. And finally, synchronously compounding the second bottom lining layer with the temperature control layer which is finished before the second bottom lining layer is compounded, so as to obtain the composite sheet.

Example 8

A composite sheet was obtained in the same manner as in example 1, except that the content of the first phase change material and the content of the first binder were changed as shown in table 1. The evaluation results are shown in table 1.

Example 9

Example 10

Then, the temperature control composition prepared in example 1 was coated on an engineering release film PET #23 (manufactured by cisselike, jiang) using a coating die without distribution ribs to form a temperature control layer having a thickness of 70 μm, and simultaneously, a peeling surface of the composite first backing layer (a surface of the first backing layer from which the PET #23 protects the release film) was laminated.

Next, the second substrate layer was coated with a full width coating die using a coater at a density of 1.35g/cm³PET #6 (trade name: PET FILM (#6) having a thermal conductivity of 0.43W/M.K, manufactured by Fushan DuPont, thickness: 6 μ M) was coated with a hot-melt pressure-sensitive adhesive B (trade name:

3520, manufactured by rhodanea), a second substrate layer was formed with a thickness of 1 μm. And finally, synchronously compounding the second bottom lining layer with the temperature control layer which is finished before the second bottom lining layer is compounded, so as to obtain the composite sheet. The evaluation results are shown in table 1.

Example 11

A composite sheet was obtained in the same manner as in example 1, except that the composition of the adhesive composition was changed as shown in table 1. The evaluation results are shown in table 1.

The adhesive composition in this example was prepared as follows: SBS (trade name: D1153E, manufactured by kraton) was dissolved with toluene to an adhesive having a solid content of 20%, and then maleic anhydride-modified alkanes (trade name: MPCM 37D, manufactured by microtek laboratories, inc.) and paraffin wax (polyethylene wax, manufactured by jingzhou gold rubber plastic) were added in an amount of 10% by mass of the total mass of the adhesive composition at a ratio of 7: 3, adding the phase change energy storage particles into the SBS adhesive, and uniformly dispersing the phase change energy storage particles by using a stirrer to obtain the adhesive composition. The particle size distribution of the formed phase change energy storage particles is 10-60 mu m, and the content of the graft modified phase change energy storage particles with the particle size distribution of less than 10 mu m in all the graft modified phase change energy storage particles is 5 vol%.

Comparative example 1

Then, the temperature control composition prepared in example 1 above was coated on an engineering release film PET #23 (manufactured by cisselike, jiang) using a coating die having uniform spaced ribs to form a phase transition region of the temperature control layer having a thickness of 80 μm, and simultaneously, a peeling surface of the composite first substrate layer (a surface of the release film protected by the peeling PET #23 of the first substrate layer) was performed.

Next, the adhesive composition prepared in example 1 was coated on an engineering release film PET #23 (manufactured by cisselike), using a mold having spaced ribs, to form adhesive regions of a temperature control layer having a thickness of 80 μm, and the filling space positions were simultaneously combined with the phase change regions of the previously combined temperature control layer, to obtain a composite sheet.

In this comparative example, the phase change regions and the adhesive regions were arranged alternately in the TD direction of the temperature control layer perpendicular to the machine direction of the composite sheet, and the area ratio of the adhesive regions to the phase change regions was 3: 1. The evaluation results are shown in table 2.

Comparative example 2

A composite sheet was obtained in the same manner as in example 1, except that the area ratio of the adhesive region to the phase change region was made 11:1 as shown in table 2. The evaluation results are shown in table 2.

Comparative example 3

Then, a coating die having uniform ribs at intervals was used to coat a temperature control composition prepared as described below on an engineering release film PET #23 (manufactured by cisseliaceae) to form a phase transition region of a temperature control layer having a thickness of 50 μm, and simultaneously, a peeling surface of the first base liner layer (a surface of the first base liner layer from which the PET #23 protects the release film) was laminated. Wherein, the temperature control composition is prepared as follows: SBS (trade name: D1153E, manufactured by Keteng) was dissolved with toluene to obtain an adhesive having a solid content of 20%, and then paraffin D (trade name: polyethylene wax, manufactured by Yangzhou gold rubber plastic) accounting for 90% of the total mass of the temperature-controlling composition was added to the SBS adhesive and uniformly dispersed using a stirrer to obtain the temperature-controlling composition.

Next, the adhesive composition prepared in example 1 above was coated on an engineering release film PET #23 (manufactured by cisselike) using a mold having spaced ribs to form adhesive regions of a temperature-controlled layer having a thickness of 50 μm, and filling space positions were simultaneously compounded with phase change regions of the previously compounded temperature-controlled layer.

In this example, the phase change regions and the adhesive regions were arranged in an alternating arrangement in the TD direction of the temperature control layer perpendicular to the machine direction of the composite sheet, and the area ratio of the adhesive regions to the phase change regions was 3: 1. The evaluation results are shown in table 2.

Comparative example 4

Coating a temperature control composition prepared as follows on an engineering release film PET #23 (manufactured by Jiangxi Sijike) by adopting a coating mould with uniform interval distribution ribs to form a phase change area of a temperature control layer with the thickness of 70 mu m, and compounding the temperature control composition as a first base material layer at the same time, wherein the density of the first base material layer is 1.35g/cm³And PET #6 (trade name: PET FILM (#6), manufactured by Fushan DuPont, thickness: 6 μ M) having a thermal conductivity of 0.43W/M.K. Wherein, the temperature control composition is prepared as follows: SBS (trade name: D1153E, manufactured by Keteng) was dissolved with toluene to a binder having a solid content of 20%, and then maleic anhydride-modified alkanes (trade name: MPCM 37D, manufactured by microtek laboratories, inc.) and paraffin wax (polyethylene wax, manufactured by Yangzhou gold rubber plastic) in an amount of 75% by mass of the total temperature control composition were mixed at a ratio of 7: 3, adding the phase change energy storage particles into the SBS adhesive, and uniformly dispersing the phase change energy storage particles by using a stirrer to obtain the temperature control composition. The particle size distribution of the formed phase change energy storage particles is 10-60 mu m, and the content of the graft modified phase change energy storage particles with the particle size distribution of less than 10 mu m in all the graft modified phase change energy storage particles is 5 vol%.

Next, the adhesive composition prepared in example 1 was coated on an engineering release film PET #23 (manufactured by cisselike) using a mold having spaced ribs to form adhesive regions of a temperature control layer having a thickness of 70 μm, and filling space positions were simultaneously compounded with phase change regions of the previously compounded temperature control layer.

Comparative example 5

A temperature control composition prepared as follows was coated on an engineering release film PET #23 (manufactured by Jiangxi Sico.) by using a coating die without distribution ribs to form a temperature control layer having a thickness of 100 μm. Then, the engineered release film PET #23 was peeled off, thereby forming a composite sheet. The evaluation results are shown in table 2.

Wherein, the temperature control composition is prepared as follows: SBS (trade name: D1153E, manufactured by Ketom) was dissolved with toluene to a binder having a solid content of 20%, and then 95% by mass of the total temperature control composition of maleic anhydride-modified alkanes (trade name: MPCM 37D, manufactured by microtek laboratories, inc.) and paraffin wax (polyethylene wax, manufactured by Yangzhou gold rubber plastic) were mixed at a ratio of 7: 3, adding the phase change energy storage particles into the SBS adhesive, and uniformly dispersing the phase change energy storage particles by using a stirrer to obtain the temperature control composition. The particle size distribution of the formed phase change energy storage particles is 10-60 mu m, and the content of the graft modified phase change energy storage particles with the particle size distribution of less than 10 mu m in all the graft modified phase change energy storage particles is 5 vol%.

TABLE 1

TABLE 2

As shown in table 1, the composite sheets of examples 1 to 11 can achieve a high phase change enthalpy value even when they have a small thickness, significantly increase the number of times of recycling, and suppress the occurrence of the flash phenomenon.

In contrast, as shown in table 2, comparative examples 1, 4 and 5 were inferior in recyclability, and comparative examples 2 and 3 were low in enthalpy of phase change heat absorption and low in heat quantity of phase change heat absorption, resulting in heat accumulation during the production of electronic components and a decrease in yield.

Industrial applicability

Claims

1. A composite sheet, comprising: a temperature control layer, a first base material layer arranged on the first surface of the temperature control layer, and a second base material layer arranged on the second surface of the temperature control layer,

the temperature control layer comprises a phase change material and a binder,

2. The composite sheet of claim 1, wherein the temperature control layer comprises:

3. A composite sheet according to claim 2, wherein the adhesive region contains a second phase change material, and the content of the second phase change material in the adhesive region is 0 to 20 mass%, preferably 5 to 15 mass%.

4. The compact of any one of claims 1-3, wherein the compact has a phase transition enthalpy of absorption of 120-200J/g;

preferably, the thickness of the composite sheet is 70-100 μm;

5. The composite sheet of any one of claims 1 to 3, wherein the first and second substrate layers have a density of 1.4g/cm³The following;

6. A composite sheet according to claim 2, wherein the thickness of the adhesive region is 40 to 80 μm, preferably 50 to 70 μm;

preferably, the width of the adhesive area is 2-10 mm, preferably 2-8 mm;

7. The composite sheet of claim 2, wherein the first adhesive has a bleed width of 1mm or less at 150 ℃ x 0.1MPa x 1H;

8. The composite sheet of claim 2, wherein the first adhesive comprises a hot melt adhesive;

preferably, the second adhesive comprises a hot melt adhesive;

preferably, the first binder has a density of 1.0g/cm³The following;

preferably, the second binder has a density of 1.0g/cm³The following;

9. The compact of claim 2, wherein the phase change material in the temperature control layer comprises graft-modified phase change energy storage particles,

10. The composite sheet according to any one of claims 1 to 3, wherein the anchoring force between the temperature control layer and the first substrate layer is 1.0 to 20.0N/10mm, and the anchoring force between the temperature control layer and the second substrate layer is 1.0 to 20.0N/10 mm;