KR20220133989A - Assembly, seat set for pressure measurement, seat - Google Patents

Abstract

The present invention provides an assembly having a sheet having a layer containing microcapsules containing a color developing agent wound around a core, wherein the breakage of the microcapsules is suppressed even when an impact due to a drop is applied. Sets and sheets are provided.
The granulated body of the present invention is a granulated body having a core and a roll of a first sheet formed by winding a long first sheet on the core, wherein the first sheet includes an elongated resin substrate and a coloring agent disposed on the resin substrate. has a first layer comprising microcapsules containing

Description

Assembly, seat set for pressure measurement, seat

The present invention relates to an assembly, a sheet set for measuring pressure, and a sheet.

In recent years, the necessity of measuring the distribution of pressure tends to increase with the increase in functionality and high definition of products.

In order to measure the distribution of pressure, a set of sheets for measuring the pressure is known. The sheet set for pressure measurement is composed of a sheet having a layer containing microcapsules containing a color developer, and a sheet having a layer containing a color developer. As described in Patent Document 1, the sheet is often transported and stored in a state wound around a core.

Japanese Patent Laid-Open No. 2009-173307

On the other hand, in recent years, with the improvement of the color development characteristic of a sheet|seat, more attention is needed in the handling of a sheet|seat. For example, when the sheet is subjected to an impact, the microcapsules are easily destroyed, and the sheet does not function as a pressure measurement sheet.

As described in Patent Document 1, the present inventors evaluated the properties of an assembly including a roll of a sheet obtained by winding a sheet having a layer containing microcapsules containing a color developer in the core as described in Patent Document 1, and as a result, at the time of conveyance and handling It turned out that microcapsules may be destroyed when the impact by the fall assumed.

In view of the above situation, the present invention provides an assembly having a sheet having a layer containing microcapsules containing a color developer wound on a core, wherein the destruction of microcapsules is suppressed even when an impact is given by dropping. The task is to provide

Moreover, this invention also makes it a subject to provide the sheet|seat set and sheet|seat for pressure measurement.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject was solvable with the following structures, as a result of earnestly examining the said subject.

(1) Dept. of authority;

A granulated body having a roll of a first sheet formed by winding a long first sheet on a winding core,

The first sheet has an elongated resin substrate and a first layer comprising microcapsules containing a coloring agent disposed on the resin substrate,

The granulation body, wherein the strength of the first sheet in the width direction is 150 mN or more.

(2) The granulated body according to (1), wherein the strength in the width direction of the first sheet is greater than the strength in the length direction of the first sheet.

(3) The granulated body according to (2), wherein the strength in the longitudinal direction of the first sheet is 180 mN or less.

(4) The granulated body according to any one of (1) to (3), wherein the strength of the first sheet in the width direction is 165 mN or more.

(5) The granulated body according to any one of (1) to (4), further comprising a pair of spacers disposed between the first sheets of the roll of the first sheet and spaced apart from each other in the width direction of the first sheet. .

(6) The granulated body according to (5), wherein the spacer has a thickness of 1 to 5 mm.

(7) The granulated body according to any one of (1) to (6), wherein the first sheet further has an adhesive layer between the resin substrate and the first layer.

(8) The granulated body according to (7), wherein the adhesive layer contains a resin having a repeating unit derived from styrene or a derivative thereof.

(9) The granulated body according to (7) or (8), wherein the thickness of the adhesive layer is 0.01 to 2.0 µm.

(10) The assembly according to any one of (1) to (9), further comprising a pair of flange members fixed to both ends of the winding core.

(11) the granulated body according to any one of (1) to (10);

A sheet set for pressure measurement having a second sheet having a second layer comprising a developer.

(12) a first sheet having an elongated resin substrate and a first layer comprising microcapsules containing a coloring agent disposed on the resin substrate;

A sheet set for pressure measurement comprising a second sheet having a second layer comprising a developer, the sheet set comprising:

The sheet set for pressure measurement, wherein the strength of the first sheet in the width direction is 150 mN or more.

(13) A sheet having an elongated resin substrate and a first layer comprising microcapsules containing a coloring agent disposed on the resin substrate,

The sheet, wherein the strength of the first sheet in the width direction is 150 mN or more.

According to the present invention, it is possible to provide an assembly having a sheet having a layer containing microcapsules containing a color developing agent wound around a core, wherein the destruction of the microcapsules is suppressed even when an impact by dropping is given. .

Further, according to the present invention, it is also possible to provide a sheet set and sheet for measuring pressure.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a perspective view showing an embodiment of an assembly of the present invention.
Fig. 2 is a perspective view showing an embodiment of a flange member.
Fig. 3 is a top view of the flange member of Fig. 3;
Fig. 4 is a perspective view showing another embodiment of the flange member.
5 is a cross-sectional view showing an embodiment of the first sheet.
Fig. 6 is a top view of the first sheet of Fig. 5;
7 is a partially enlarged cross-sectional view of the first sheet.

Hereinafter, the present invention will be described in detail.

In addition, the numerical range shown using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

In addition, in the numerical range described step by step in this specification, the upper limit or lower limit described in a certain numerical range may be substituted with the upper limit or lower limit of the numerical range of another stepwise description. In addition, in the numerical range described in this specification, you may substitute the value shown in the Example for the upper limit or lower limit described in a certain numerical range.

You may use the various components mentioned later individually by 1 type or in mixture of 2 or more types. For example, the polyisocyanate mentioned later may be used individually by 1 type or in mixture of 2 or more types.

A characteristic point of the granulated body of the present invention is that the strength in the width direction of the first sheet wound around the core is adjusted.

The details of the reason why the desired effect is obtained by adjusting the strength is not clear, but when the strength is greater than or equal to a predetermined value during collision by dropping, even if an impact is applied to the roll of the first sheet, the thickness of the first sheet in the width direction is It is thought that the deformation of the first layer is suppressed by suppressing the deformation, and consequently, the destruction of the microcapsule is suppressed.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a perspective view showing an embodiment of an assembly of the present invention.

The assembly 10 includes a hollow cylindrical core 12, a pair of flange members 14 fixed to both ends of the core 12, and a long first sheet described later on the winding core 12 by winding it. It has the roll 16 of the 1st sheet|seat formed.

In FIG. 2, the perspective view of the flange member 14 shown in FIG. 1 is shown. In FIG. 3, the top view of the flange member 14 is shown. The flange member 14 has a substrate (flange) 18 , an insertion portion 20 disposed on the substrate 18 , and a projection 22 disposed on a surface (outer peripheral surface) of the insertion portion 20 . .

The insertion portion 20 of the flange member 14 can be inserted into the hollow portion of the hollow cylindrical core 12 . In FIG. 1 , the insertion portion 20 of the flange member 14 is inserted into the hollow portion of the core 12 , and the projection 22 of the insertion portion 20 comes into contact with the inner circumferential surface of the core 12 . (12) and the flange member (14) are fixed.

Hereinafter, each member is described in detail.

<Gwonsim (12)>

A first sheet is wound around the core 12 .

Plastic, paper, wood, and metal are mentioned as a material of the winding core 12. As shown in FIG. Among them, paper is preferable because the fixing strength between the core and the flange member can be appropriately adjusted. Examples of the paper include paper tube base paper and paper impregnated with resin.

Although the size in particular of the winding core 12 is not restrict|limited, 50-350 mm is preferable and, as for an outer diameter (the diameter of the outer side of a winding core), 85-90 mm is more preferable.

In addition, when the winding core has a shape other than a cylindrical shape, the outer diameter corresponds to the diameter of the circumscribed circle of the winding core.

45-345 mm is preferable and, as for the inner diameter of the cylindrical core 12, 80-85 mm is more preferable.

In addition, although the core 12 is a hollow cylindrical shape in FIG. 1, if a 1st sheet|seat can be wound, it will not be limited to the aspect of the shape.

For example, the core may have a polygonal columnar shape. In addition, the core may be solid.

<Flange member (14)>

The flange member 14 is being fixed to both ends of the winding core 12 . As described above, in FIG. 1 , the core 12 and the flange member 14 are fixed when the protrusion 22 in the flange member 14 comes into contact with the inner peripheral surface of the core 12 .

As a material of the flange member 14, plastics, paper, wood, and a metal are mentioned. Among them, plastic is preferable. Examples of the plastic include polypropylene, polyethylene, and polyethylene terephthalate, and polypropylene is preferable.

In addition, it is preferable that the insertion part 20 and the protrusion part 22 mentioned later are also comprised with the said material.

The flange member 14 includes a substrate 18 .

In FIG. 2, although the board|substrate 18 is an octagonal shape, the shape in particular is not restrict|limited, A circular shape may be sufficient, and other polygonal shapes other than an octagonal shape (for example, a hexagonal shape) may be sufficient.

Although the thickness in particular of the board|substrate 18 is not restrict|limited, 1-50 mm is preferable, and 2-20 mm is more preferable.

Although the size in particular of the board|substrate 18 is not restrict|limited, Usually, it is preferable that it is larger than the outer diameter of the roll 16 of 1st sheet|seat. In addition, the size of the substrate 18 means the diameter of the circumscribed circle of the substrate 18 .

It is preferable that it is 1 mm or more larger than the roll 16 of a 1st sheet, and, as for the magnitude|size of the board|substrate 18, it is more preferable that it is 5 mm or more larger. Although the upper limit is not particularly limited, it is often 600 mm or less.

The flange member 14 has an insert 20 disposed on the substrate 18 . The insertion portion 20 is a member extending along the normal direction of the substrate 18 .

Although the length in particular along the extending direction of the insertion part 20 is not restrict|limited, 2-100 mm is preferable, and 20-30 mm is more preferable.

Although the insertion part 20 shown in FIGS. 2 and 3 is cylindrical shape, if it can insert in the hollow part of the winding core 12, it will not be limited to this form, For example, the shape of the insertion part may be polygonal.

It is preferable that the outer diameter of the insertion part 20 (the diameter of the outer side of the insertion part 20) is smaller than the inner diameter of the winding core 12. As shown in FIG. 45-345 mm is preferable and, as for the outer diameter of the insertion part 20, 80-85 mm is more preferable.

On the outer peripheral surface of the insertion part 20, the projection part 22 is arrange|positioned. 2-3, although the number of the projection parts 22 is three, the number in particular is not restrict|limited, Four or more may be sufficient. The number of the protrusions 22 is preferably 3 or more, from the viewpoint that the destruction of the microcapsule is more suppressed (hereinafter, also simply referred to as "the point where the effect of the present invention is more excellent") even when an impact by falling is given. and 4 or more are more preferable. The upper limit is not particularly limited, and is often 100 or less.

As shown in FIG. 3 , the three projections 22 are arranged at equal intervals on the outer peripheral surface of the insertion portion 20 . Although the arrangement position of the projections is not limited to the embodiment of Fig. 3, when there are a plurality of projections, it is preferable that the plurality of projections are arranged at equal intervals on the outer peripheral surface of the insertion portion.

As shown in FIG. 3 , the three projections 22 are arranged so as to be in contact with the substrate 18 . Although the relationship between the distance between a projection part and a board|substrate is not limited to the aspect of FIG. 3, It is preferable that the distance between a some projection part and a board|substrate is respectively equal. That is, it is preferable that the distance between a projection part and a board|substrate is the same in each projection part.

2 and 3, although the shape of the projection part 22 is rectangular, the shape in particular is not restrict|limited.

The height of the protrusion 22 (height from the outer circumferential surface of the inserting section 20) is not particularly limited, and when the inserting section 20 is inserted into the hollow of the core 12, the protrusion on the inner circumferential surface of the core 12 is It is not particularly limited as long as it is the height at which (22) is in contact. Especially, 0.1-5 mm is preferable, 0.5-2 mm is more preferable, 0.5-1.5 mm is still more preferable.

In addition, the height of a projection part may be constant and may differ according to a position. For example, since the effect of this invention is more excellent, the direction orthogonal to the direction in which a projection part extends WHEREIN: The height of a projection part may become low toward the edge part of a projection part.

Although the width in particular in the direction orthogonal to the direction in which the projection part 22 extends is not restrict|limited, 1-25 mm is preferable, and 5-10 mm is more preferable.

In addition, the flange member is not limited to the form of FIG. 2 and FIG. 3, For example, as shown in FIG. 4, the hole 40 may be formed in the board|substrate 180 contained in the flange member 140. . By passing a finger through the hole 40, the assembly can be easily transported without dropping it. In FIG. 4, although eight hole parts 40 are formed, the number in particular is not restrict|limited, One may be sufficient as it, and it may be plural.

<Roll of 1st sheet>

The roll 16 of the 1st sheet|seat is a wound material which consists of a 1st sheet|seat, formed by winding a 1st sheet|seat on the core. The first sheet is in the shape of a long picture. Long picture means that the length in the longitudinal direction is longer than the length in the width direction.

Fig. 5 is a cross-sectional view in the width direction of one embodiment of the first sheet, and Fig. 6 is a top view of the first sheet in Fig. 5 .

The first sheet 24 shown in FIGS. 5 and 6 includes a support 26 , an adhesive layer 28 disposed on the support 26 , and a first layer 30 disposed on the adhesive layer 28 . has 5 and 6 , a pair of spacers 32 is disposed on the first sheet 24 . As shown in FIGS. 5 and 6 , a pair of spacers 32 are arranged to be spaced apart from each other in the width direction of the first sheet 24 . In the case of such an aspect, when the first sheet 24 is wound around the core, the first layer 30 and the first layer 30 are positioned on the opposite side to the winding core side due to the presence of the spacer 32 . It is possible to suppress contact of the supporting body 26 to be used, and it is possible to further suppress the destruction of the microcapsules in the first layer 30 . Therefore, it is preferable that the granulated body further has a pair of spacers disposed between the first sheets of the roll of the first sheet and spaced apart from each other in the width direction of the first sheet.

In addition, although the 1st sheet|seat 24 shown in said FIG. 5 and 6 included the adhesive layer 28, this invention is not limited to this form, The 1st sheet|seat does not need to include an adhesive layer.

In addition, although the spacer 32 is arrange|positioned on the 1st sheet|seat 24 shown in said FIG. 5 and 6, this invention is not limited to this form, The assembly does not need to include a spacer.

Moreover, the intensity|strength in the width direction of a 1st sheet|seat is 150 mN or more. Especially, from the point which the effect of this invention is more excellent, 153 mN or more is preferable, 165 mN or more is more preferable, 170 mN or more is still more preferable, 175 mN or more is especially preferable. When the strength in the width direction of the first sheet is 165 mN or more, the microcapsules are destroyed even in the first sheet having a first layer containing the microcapsules which are easily broken, corresponding to the micro pressure that develops color at 0.2 MPa or less. hard to be If the strength in the width direction of the first sheet is 175 mN or more, the microcapsules are not destroyed even in the first sheet having a first layer containing microcapsules that are more easily broken in response to the ultra-micro pressure that develops at 0.05 MPa or less. difficult. Although the upper limit is not particularly limited, it is often 500 mN or less.

The strength in the longitudinal direction of the first sheet is not particularly limited, but 180 mN or less is preferable, and 170 mN or less is more preferable from the viewpoint of more excellent effects of the present invention. Although a minimum in particular is not restrict|limited, From the point of manufacturing aptitude, 100 mN or more is preferable, and 130 mN or more is more preferable.

Especially, since the effect of this invention is more excellent, it is preferable that the intensity|strength of the width direction of a 1st sheet|seat is larger than the intensity|strength of the longitudinal direction of a 1st sheet|seat.

The ratio of the strength in the width direction of the first sheet to the strength in the length direction of the first sheet (strength in the width direction/strength in the length direction) is not particularly limited, and is often 0.90 or more, and the effect of the present invention is more From an excellent point, 1.00 or more are preferable, 1.20 or more are more preferable, and 1.22 or more are still more preferable. Although an upper limit in particular is not restrict|limited, There are many cases where it is 1.50 or less, and there are more cases where it is 1.40 or less.

The measuring method of the said intensity|strength is as follows.

From the first sheet, a test piece of 200 mm in the longitudinal direction (vertical direction) and 15 mm in the width direction (horizontal direction) was cut out, and using a LOOP STIFFNESS TESTER (manufactured by Toyo Seiki Seisakusho Co., Ltd.), measure the strength. The measurement conditions were a clamp interval distance of 100 mm, a loop length of 85 mm, and a compression rate of 3.3 mm/sec. The above measurement is performed on two test pieces, the average value of the strength in the longitudinal direction obtained from the two test pieces is taken as the strength in the longitudinal direction of the first sheet, and the average value of the strength in the width direction obtained from the two test pieces is used as the first Let it be the strength in the width direction of a sheet|seat. In addition, when measuring the strength in the longitudinal direction of the first sheet, a test piece cut out so that the longitudinal direction of the test piece follows the longitudinal direction of the first sheet is used, and when measuring the strength in the width direction of the first sheet, the The test piece cut out so that the longitudinal direction may follow the width direction of a 1st sheet|seat is used.

In addition, the strength in the width direction and the length direction of the first sheet can be appropriately adjusted according to the type of member constituting the first sheet, the manufacturing method of the first sheet, and the like. For example, when the first sheet includes an adhesive layer, by adjusting the thickness and number of layers of the adhesive layer, the presence or absence of particles having the adhesive layer, the type of particles, the hardness of the particles, the size of the particles, and the amount of particles, The strength of the first sheet can be adjusted. In addition to the above, the strength of the first sheet can be adjusted by adjusting the presence or absence of particles of the resin substrate, the type of particles, the hardness of the particles, the size of the particles, and the amount of the particles. Moreover, the intensity|strength of a 1st sheet|seat can be adjusted by adjusting the order of the extending|stretching process at the time of manufacturing a 1st sheet|seat. In addition, the strength of the resin substrate can be adjusted by adjusting the type and manufacturing conditions of the resin substrate to be used, and as a result, the strength of the first sheet can be adjusted.

Hereinafter, each member (resin base material, adhesive layer, 1st layer, spacer) is demonstrated in detail.

(resin substrate)

The first sheet includes a long resin substrate. The resin substrate is a member for supporting the first layer.

The elongate resin substrate means a resin substrate whose length in the longitudinal direction is longer than the length in the width direction.

Although the width|variety in particular of a resin base material is not restrict|limited, In many cases, it is 50-1500 mm, and 50-500 mm is preferable.

The resin substrate is not particularly limited as long as the first sheet satisfies predetermined strength characteristics, but a polyester film such as a polyethylene terephthalate film, a cellulose derivative film such as cellulose triacetate, and polyolefin such as polypropylene and polyethylene A film and a polystyrene film are mentioned.

Although the thickness in particular of a resin base material is not restrict|limited, From the point which the effect of this invention is more excellent, 10-200 micrometers is preferable.

It is preferable that the resin base material contains particle|grains from the point which makes the intensity|strength of the width direction of a 1st sheet|seat 150 mN or more, and the point which makes roll-shaped sheet|seat conveyance favorable.

Examples of the particles include calcium carbonate particles, calcium phosphate particles, silica particles, crystalline glass filler particles, kaolin particles, talc particles, titanium dioxide particles, alumina particles, silica-alumina composite oxide particles, barium sulfate particles, calcium fluoride particles, fluoride particles. inorganic particles such as lithium particles, zeolite particles, molybdenum sulfide particles, and mica particles; and organic particles such as polystyrene particles, acrylic resin particles, methyl methacrylate particles, benzoguanamine/formaldehyde condensate particles, melamine/formaldehyde condensate particles, and polytetrafluoroethylene particles.

The resin substrate is appropriately selected so that the first sheet exhibits a predetermined strength.

In addition, the intensity|strength of the longitudinal direction and the width direction of a resin base material can be adjusted by controlling manufacturing conditions, when manufacturing a resin base material by a well-known method (extrusion molding).

As a manufacturing method of a resin base material, you may have the process of extending|stretching (for example, biaxial stretching) an unstretched film. In addition, the manufacturing method of a resin base material may have a heat setting process and a thermal relaxation process. In addition, as a manufacturing method of a resin base material, the method of Paragraph 0063 of Unexamined-Japanese-Patent No. 2011-208125 - 0125 is applicable.

As an aspect, it is preferable that the resin base material in this invention does not contain a coarse particle, a foreign material, a defect, a precipitate, etc. It is preferable that it is 50 pieces/10 mm< ² > or less, and, as for the number of coarse particles 5 micrometers or more in diameter, a foreign material, and a defect, it is more preferable that it is 10 pieces/10 mm< ² > or less.

(Adhesive layer)

An adhesion layer is a layer for improving the adhesiveness between a resin base material and a 1st layer.

From the viewpoint of more excellent effects of the present invention, it is preferable that the adhesion layer is a resin layer containing a resin, the material of the capsule wall of the microcapsule is composed of a resin, and the adhesion layer is a resin layer containing a resin desirable. In particular, when the binder contained in the first layer is small, the microcapsules may agglomerate when the composition having microcapsules is applied and dried. When the adhesive layer is a resin layer, as shown in FIG. 7 , the microcapsules 34 included in the first layer 30 interact with the adhesive layer 28 on the resin substrate 26, so that the microcapsules 34 Since aggregation of each other is suppressed and the microcapsules 34 can be stably present in a dispersed state on the adhesion layer 28, the color development granularity is improved during pressure measurement.

Although the material constituting the adhesive layer is not particularly limited, for example, styrene butadiene resin, styrene (meth) acrylic resin, (meth) acrylic resin, olefin resin, urethane resin, polyester resin, and polyvinyl alcohol resin are mentioned. can Especially, a styrene-butadiene resin, a styrene (meth)acrylic resin, or a (meth)acrylic resin is more preferable at the point which is more excellent in the adhesiveness of a resin base material and a 1st layer.

Especially, it is preferable that the adhesive layer contains resin which has a repeating unit derived from styrene or its derivative(s) from the point which the effect of this invention is more excellent. In particular, when the material of the capsule wall of the microcapsule has an aromatic structure, if the adhesive layer has an aromatic structure, the color development granularity becomes better.

The resin having a repeating unit derived from styrene or a derivative thereof may contain repeating units other than the repeating unit derived from styrene or a derivative thereof.

Although content in particular of the repeating unit derived from styrene or its derivative(s) in resin which has repeating unit derived from styrene or its derivative(s) is not restrict|limited, 5-100 mass % with respect to all the repeating units is preferable.

The styrene derivative means a compound in which a substituent (eg, an alkyl group, an alkoxy group, a carboxyl group, or a halogen atom) is substituted at the alpha, ortho, meta or para position of styrene.

Although the thickness in particular of an adhesive layer is not restrict|limited, The lower limit is 0.01 micrometer or more in many cases, and 0.04 micrometer or more is preferable at the point which the effect of this invention is more excellent. The upper limit is often 5 µm or less, and from the viewpoint of more excellent effects of the present invention, 3 µm or less is preferable, and from the viewpoint of more excellent color development and granularity when used as a sheet for pressure measurement, 2.0 µm or less is more preferable do.

A single layer structure may be sufficient as an adhesive layer, and a multilayer structure may be sufficient as it. When the adhesive layer has a multilayer structure, it is preferable that the total thickness of the adhesive layer is within the above range.

In addition, the adhesion layer may contain other materials other than resin mentioned above. Other materials include, for example, inorganic particles and organic particles. As an inorganic particle and an organic particle, the thing similar to the particle|grains which the above-mentioned resin base material may contain is mentioned. The particles may be particles having antistatic properties. In addition, two or more types of particle|grains may be used and it may contain it in both of a resin base material and an adhesive layer.

It is preferable that at least either one of a resin base material and an adhesive layer contains particle|grains from the point which the effect of this invention is more excellent. When at least one of the resin substrate and the adhesion layer contains particles, the strength of the first sheet in the width direction is easily adjusted to 150 mN or more.

From the viewpoint of adjusting the strength in the width direction of the first sheet to 150 mN or more, it is preferable that the particle size of the particles contained in any of the resin substrate and the adhesion layer is large. Specifically, it is preferable that the ratio of inorganic particles having a particle diameter of 1 µm or more to the entire inorganic particle is 50% by volume or more, and more preferably 50% by volume or more of inorganic particles of 10 µm or more.

When any of the resin substrate and the adhesive layer contains inorganic particles and resin, the ratio of inorganic particles having a particle diameter of 1 µm or more and the ratio of inorganic particles having a particle diameter of 10 µm or more to the entire inorganic particles are calculated as follows.

By baking the resin base material (in the case of having an adhesion layer, the resin base material and the adhesion layer, the same hereinafter), at least a part of the resin is decomposed and removed from the resin base material, and the inorganic particles are left. The remaining inorganic particles are dispersed in ethanol. With respect to the inorganic particles contained in the obtained dispersion, a laser diffraction particle size distribution analyzer (for example, Mastersizer2000 manufactured by Malvern, Laser diffraction/scattering particle size distribution analyzer LA-920 manufactured by Horiba Corporation) is used, The volume-based particle size distribution is obtained by the wet method. From the obtained particle size distribution, the ratio (volume %) of the inorganic particle which occupies for the whole inorganic particle with a particle diameter of 1 micrometer or more is calculated|required.

The method for forming the adhesion layer is not particularly limited, and examples thereof include a method of applying a composition for forming an adhesion layer to a resin substrate, and a method of forming the adhesion layer forming material by co-extrusion with the material for forming a resin substrate. .

In addition, as a method of forming the adhesion layer, a method of applying a composition for forming an adhesion layer on the surface of the biaxially stretched resin substrate, and the surface of the resin substrate stretched in the first direction (eg, MD: Machine Direction) After applying the composition for forming an adhesion layer to the resin substrate in a second direction (eg, TD: Transverse Direction) orthogonal to the first direction along the surface of the resin substrate, the coating material of the composition for forming the adhesion layer is applied to the resin substrate The method of extending|stretching together is also mentioned.

(1st floor)

The first layer includes microcapsules containing a coloring agent.

Hereinafter, first, the material constituting the microcapsule will be described in detail.

A microcapsule generally has a core part and a capsule wall for enclosing the core material (included thing (it is also called an encapsulation component)) constituting the core part.

In the present invention, the microcapsule contains a coloring agent as a core material (inclusion component). Since the coloring agent is encapsulated in the microcapsule, the coloring agent can be stably present until the microcapsule is destroyed by pressurization.

The microcapsule has a capsule wall containing a core material.

As the material (wall material) for the capsule wall of the microcapsule, a known resin conventionally used as a wall material for the microcapsule containing a color-developing agent in the use of pressure-sensitive copy paper or thermal recording paper can be mentioned. Specific examples of the resin include polyurethane, polyurea, polyurethaneurea, melamine-formaldehyde resin, and gelatin.

Among them, from the viewpoint of more excellent effects of the present invention, it is preferable that the capsule wall of the microcapsule contains at least one resin selected from the group consisting of polyurethaneurea, polyurethane and polyurea.

The capsule wall of the microcapsule is preferably substantially composed of resin. Being substantially comprised of resin means that content of resin with respect to the total mass of capsule wall is 90 mass % or more, and 100 mass % is preferable. That is, it is preferable that the capsule wall of a microcapsule is comprised with resin.

In addition, polyurethane is a polymer which has a plurality of urethane bonds, and it is preferable that it is a reaction product formed from the raw material containing a polyol and polyisocyanate.

Moreover, it is preferable that polyurea is a polymer which has a plurality of urea bonds, and is a reaction product formed from the raw material containing polyamine and polyisocyanate. Moreover, polyurea can also be synthesize|combined using polyisocyanate and not using a polyamine by using that a part of polyisocyanate reacts with water to become a polyamine.

In addition, polyurethane urea is a polymer having a urethane bond and a urea bond, and is preferably a reaction product formed from a raw material containing a polyol, a polyamine, and a polyisocyanate. Moreover, when making a polyol and polyisocyanate react, a part of polyisocyanate reacts with water to become a polyamine, and polyurethaneurea may be obtained as a result.

Moreover, it is preferable that a melamine-formaldehyde resin is a reaction product formed from polycondensation of melamine and formaldehyde.

Moreover, the said polyisocyanate is a compound which has two or more isocyanate groups, An aromatic polyisocyanate and aliphatic polyisocyanate are mentioned. As polyisocyanate, the adduct body (adduct) of polyols, such as a trimethylol propane, and bifunctional polyisocyanate may be sufficient, for example.

In addition, the polyol is a compound having two or more hydroxyl groups, for example, a low molecular weight polyol (eg, an aliphatic polyol, an aromatic polyol. In addition, "low molecular weight polyol" means a polyol having a molecular weight of 400 or less) , polyvinyl alcohol, polyether-based polyol, polyester-based polyol, polylactone-based polyol, castor oil-based polyol, polyolefin-based polyol, and hydroxyl group-containing amine-based compounds (eg, amino alcohol. Examples of amino alcohols include: For example, N,N,N',N'-tetrakis[2-hydroxypropyl]ethylenediamine etc. which are propylene oxide or ethylene oxide adducts of amino compounds, such as ethylenediamine, are mentioned.) is mentioned. have.

In addition, the said polyamine is a compound which has two or more amino groups (a primary amino group or secondary amino group), For example, diethylenetriamine, triethylenetetramine, 1, 3- propylenediamine, and hexamethylene aliphatic polyvalent amines such as diamine; Epoxy compound adduct of aliphatic polyhydric amine; alicyclic polyvalent amines such as piperazine; and heterocyclic diamines such as 3,9-bis-aminopropyl-2,4,8,10-tetraoxaspiro-(5,5)undecane.

Although the glass transition temperature in particular of the capsule wall of a microcapsule is not restrict|limited, 50-160 degreeC is preferable, and 80-150 degreeC is more preferable.

The measurement method of the glass transition temperature of the said capsule wall is as follows.

Fifty first sheets of length 1 cm x width 1 cm are prepared, all immersed in 10 ml of water, and left still for 24 hours to obtain an aqueous dispersion of microcapsules.

The obtained aqueous dispersion of microcapsules is centrifuged at 15000 rpm for 30 minutes, and the microcapsules are aliquoted. Ethyl acetate was added to the aliquoted microcapsules, and the mixture was further stirred at 25°C for 24 hours. Then, the obtained solution is filtered, and the obtained residue is vacuum-dried at 60 degreeC for 48 hours, and microcapsules containing nothing inside (hereafter simply referred to as "measurement material") are obtained. That is, the capsule wall material of microcapsules which is the measurement object of a glass transition temperature is obtained.

Next, the thermal decomposition temperature of the obtained measurement material is measured using the thermogravimetric differential thermal analysis apparatus TG-DTA (device name: DTG-60, Shimadzu Corporation). In addition, the thermal decomposition temperature means that, in thermogravimetric analysis (TGA) of the atmospheric atmosphere, the measurement material is heated from room temperature at a constant temperature increase rate (10° C./min), and the mass of the measurement material before heating is reduced by 5% by mass. Let it be the thermal decomposition temperature (°C) with the temperature at the time.

Next, the glass transition temperature of the measurement material is measured using a differential scanning calorimeter DSC (device name: DSC-60a Plus, Shimadzu Corporation) using an airtight fan at a temperature increase rate of 5°C/min from 25°C to ( It is measured in the range of thermal decomposition temperature (°C)-5°C). As the glass transition temperature of the capsule wall of the microcapsule, the value at the time of temperature increase in the second cycle is used.

Although the average particle diameter in particular of a microcapsule is not restrict|limited, The median diameter (D50) on a volume basis is preferably from 1 to 80 µm, more preferably from 5 to 70 µm, still more preferably from 10 to 50 µm.

The volume-based median diameter of the microcapsules can be controlled by adjusting the conditions for producing the microcapsules and the like.

Here, the volume-based median diameter of the microcapsule refers to a diameter in which the sum of the volumes of the particles on the large-diameter side and the small-diameter side is equivalent when the particle diameter at which the total volume of the entire microcapsule is 50% is divided by a threshold value. . That is, the median diameter corresponds to so-called D50.

It is a value calculated by photographing the surface of the first layer of the first sheet having the first layer containing microcapsules at a magnification of 1000 with an optical microscope, and measuring the sizes of all microcapsules in the range of 500 μm×500 μm. .

The number average wall thickness of the microcapsules (number average wall thickness of the capsule wall of the microcapsules) is not particularly limited, but is preferably 0.01 µm or more and 2 µm or less, more preferably more than 0.02 µm and less than 2 µm, and more preferably 0.05 µm or more and 1.5 µm or more. ㎛ or less is more preferable.

In addition, the wall thickness of microcapsules refers to the thickness (μm) of the capsule walls forming the capsule particles of the microcapsules, and the number average wall thickness refers to the thickness (μm) of individual capsule walls of the five microcapsules. It means the average value calculated|required with the electron microscope (SEM) and averaged. More specifically, a cross-section of the first sheet having a first layer containing microcapsules is prepared, and the cross-section is observed at 200 times by SEM, (value of average particle diameter of microcapsules) x 0.9 to (microcapsules) After selecting 5 random microcapsules having a long diameter in the range of (average particle diameter) × 1.1, the cross-section of each selected microcapsule is observed at 15000 times to find the thickness of the capsule wall and calculate the average value. In addition, the long diameter means the longest diameter when microcapsules are observed.

The ratio (δ/Dm) of the number average wall thickness (δ) of the microcapsules to the average particle diameter (Dm) of the microcapsules is not particularly limited, and is often 0.001 or more. Especially, it is preferable to satisfy|fill the relationship of Formula (1) at the point which the effect of this invention is more excellent.

Formula (1) 0.100 > δ/Dm > 0.001

That is, it is preferable that the said ratio (delta/Dm) is larger than 0.001 and less than 0.100. If the relationship of formula (1) is satisfied, the color development density gradation can be made into a range that is easy to recognize depending on the pressure.

[Color developer]

Inside the microcapsules, a coloring agent is contained.

A coloring agent is a compound which develops color by contacting with the coloring agent mentioned later in a colorless state. As the color developer, an electron-donating dye precursor (precursor of a color-developing dye) is preferable. That is, as a color developing agent, an electron-donating colorless dye is preferable. As the color developing agent, a known color developer can be used for use in pressure-sensitive copy paper or thermal recording paper. Examples of the coloring agent include a triphenylmethane phthalide compound, a fluoran compound, a phenothiazine compound, an indolyl phthalide compound, an azaindolyl phthalide compound, a leukoramine compound, and rhodamine lactam. compounds, triphenylmethane compounds, diphenylmethane compounds, triazine compounds, spiropyran compounds, and fluorene compounds.

As said compound, the compound of Unexamined-Japanese-Patent No. 5-257272, the compound of paragraphs 0030 - 0033 of International Publication No. 2009/8248, 3',6'-bis(diethylamino)-2-( 4-Nitrophenyl)spiro[isoindole-1,9'-xanthene]-3-one, 6'-(diethylamino)-1',3'-dimethylfluoran, and 3,3-bis(2 -methyl-1-octyl-3-indolyl)phthalide.

The molecular weight in particular of a coloring agent is not restrict|limited, 300 or more are preferable. Although the upper limit in particular is not restrict|limited, 1000 or less are preferable.

[Other Ingredients]

The microcapsule may contain other components other than the above-mentioned coloring agent.

For example, it is preferable that the microcapsule contains a solvent.

The solvent is not particularly limited, and for example, an alkylnaphthalene-based compound such as diisopropylnaphthalene, a diarylalkane-based compound such as 1-phenyl-1-xylylethane, and an alkylbiphenyl-based compound such as isopropylbiphenyl Aromatic hydrocarbons, such as a triarylmethane type compound, an alkylbenzene type compound, a benzyl naphthalene type compound, a diarylalkylene type compound, and an aryl phosphorus compound; aliphatic hydrocarbons such as dibutyl phthalate and isoparaffin; and natural animal and vegetable oils such as soybean oil, corn oil, cottonseed oil, rapeseed oil, olive oil, palm oil, castor oil, and fish oil, and natural product high boiling point oil such as mineral oil.

When the solvent is contained in the microcapsule, the mass ratio of the solvent and the color developer (mass of the solvent/mass of the color developer) is preferably in the range of 98/2 to 30/70, and 97/3 to 40/60 from the viewpoint of color development. The range of is more preferable.

In addition to the above-mentioned components, the microcapsule may contain one or more types of additives, such as a ultraviolet absorber, a light stabilizer, antioxidant, a wax, and an odor inhibitor, as needed.

[Method for producing microcapsules]

The method for producing the microcapsules is not particularly limited, and, for example, known methods such as interfacial polymerization, internal polymerization, phase separation, external polymerization, and coacervation may be used. Especially, the interfacial polymerization method is preferable.

Hereinafter, the interfacial polymerization method will be described, taking as an example a method for producing microcapsules whose capsule wall is polyurea or polyurethaneurea.

As the interfacial polymerization method, a color developer, a solvent having a boiling point of 100° C. or higher, and a capsule wall material (for example, a raw material containing at least one selected from the group consisting of polyisocyanate, polyol, and polyamine. In addition, polyisocyanate and water A step of dispersing an oil phase containing an emulsifier in an aqueous phase containing an emulsifier (emulsification step) to prepare an emulsion (emulsification step); An interfacial polymerization method comprising a step (encapsulation step) of forming a capsule wall by polymerization at the interface between an aqueous phase and a color developing agent-containing microcapsule is preferable.

In addition, the mass ratio of the total amount of polyol and polyamine and the amount of polyisocyanate in the raw material (total amount of polyol and polyamine/amount of polyisocyanate) is not particularly limited, but 0.1/99.9 to 30/70 is preferable, 1/99 - 25/75 are more preferable.

In addition, the kind in particular of the emulsifier used in the said emulsification process is not restrict|limited, For example, a dispersing agent and surfactant are mentioned.

As a dispersing agent, polyvinyl alcohol is mentioned, for example.

The 1st layer may contain other components (for example, binder, surfactant) other than the microcapsule mentioned above.

In addition, although the mass (g/m2) in particular of a ^1st layer is not restrict|limited, From the point which the effect of this invention is more excellent, ^0.5-30 g/m2 is preferable.

(Method of forming the first layer)

The formation method in particular of the said 1st layer is not restrict|limited.

For example, the method of apply|coating the composition for 1st layer formation containing microcapsules on the resin base material (or on the adhesion layer), and heat-processing a predetermined temperature or more with respect to the obtained coating film is mentioned.

In addition to the above, a method of separately preparing microcapsules and applying a composition for forming the first layer containing microcapsules on a resin substrate (or on an adhesion layer) is also mentioned.

Hereinafter, an aspect of heating at a predetermined temperature or higher will be described in detail.

It is preferable that at least a microcapsule and a solvent are contained in the composition for 1st layer formation. Moreover, you may use the microcapsule dispersion liquid obtained by the above-mentioned interfacial polymerization method as a composition for 1st layer formation.

The other component which may be contained in the 1st layer mentioned above may be contained in the composition for 1st layer formation.

The method of applying the composition for forming the first layer is not particularly limited, and examples of the coater used at the time of application include an air knife coater, a rod coater, a bar coater, a curtain coater, a gravure coater, an extrusion coater, a die coater, a slide bead coater, and a blade coater.

After apply|coating the composition for 1st layer formation on the resin base material (or on the adhesion layer), the obtained coating film is heat-processed more than predetermined temperature.

As the temperature condition for the heat treatment, an optimum temperature is selected depending on the material of the capsule wall of the microcapsule used, but from the viewpoint of more excellent effects of the present invention, preferably 60°C or higher, and more preferably 70°C or higher . Although the upper limit in particular is not restrict|limited, 140 degrees C or less is preferable and 120 degrees C or less is more preferable at the point which is 180 degrees C or less in many cases, and the color development density is more excellent.

Although the heating time in particular is not restrict|limited, From the point which the effect of this invention is more excellent and the point of productivity, 1.0 to 20 minutes are preferable, and 3.0 to 10 minutes are more preferable.

In addition, in the above, the method of forming the first layer on the resin substrate (or on the adhesion layer) has been described, but it is not limited to the above aspect, for example, after forming the first layer on the temporary support, You may transcribe|transfer a 1st layer on a resin base material.

As a temporary support body, if it is a peelable support body, it will not restrict|limit especially.

(spacer)

The material of the spacer is not particularly limited, but a rubber foam or an elastic foam is preferred. Examples of the rubber foam include a rubber foam selected from the group consisting of natural rubber, isoprene rubber, styrene rubber, nitrile rubber, butadiene rubber, chloroprene rubber, and urethane rubber. Examples of the elastic foam include an elastic foam selected from the group consisting of polyethylene, polypropylene, polystyrene, polyvinyl chloride, and polyvinyl acetate.

The thickness of the spacer is not particularly limited, but is preferably thicker than the first layer.

The thickness of the spacer is 1 to 10 mm in many cases, and from the point where the effect of this invention is more excellent, 1-5 mm is preferable and 2.5-5 mm is more preferable.

Although the static friction coefficient in particular of a spacer is not restrict|limited, From the point which the effect of this invention is more excellent, 0.1-1.0 is preferable.

Although the dynamic friction coefficient in particular of a spacer is not restrict|limited, From the point which the effect of this invention is more excellent, 0.1-1.0 is preferable.

The method of disposing the spacer on the first sheet is not particularly limited, and examples include a method using a double-sided tape and a method using an adhesive or a pressure-sensitive adhesive.

The arithmetic mean roughness (Ra) of the first sheet is not particularly limited, and in many cases is 0.1 µm or more, and is preferably 2.5 to 7.0 µm from the viewpoint of more excellent color development density. In addition, the arithmetic mean roughness Ra of the first sheet is intended to mean the arithmetic mean roughness Ra of the surface of the first sheet on the side opposite (contacting side) to the second sheet when the sheet set for pressure measurement is used. . When the first layer is located on the outermost surface of the first sheet on the side opposite to the second sheet, the arithmetic mean roughness (Ra) is the arithmetic mean roughness (Ra) of the surface of the first layer opposite to the resin substrate side. ) corresponds to

In this specification, the arithmetic mean roughness (Ra) (the arithmetic mean roughness (Ra) of the first sheet and the arithmetic mean roughness (Ra) of the second sheet to be described later) is defined in JIS B 0681-6:2014. It means the arithmetic mean roughness (Ra). In addition, as a measuring apparatus, the scanning type white interferometer using the optical interference method (in detail, NewView5020 by Zygo Corporation; objective lens x 50 times; intermediate lens x 0.5 times) is used. The measurement mode in the case of measuring the arithmetic mean roughness (Ra) of the first sheet using the scanning white interferometer is the Stich mode, and the measurement mode in the case of measuring the arithmetic mean roughness (Ra) of the second sheet is the Micro mode to be.

Moreover, in the granulated body 10 shown in FIGS. 1-3, the insertion part 20 of the flange member 14 was inserted into the hollow part of the winding core 12, and both were fixed. is not limited to

For example, there is a protrusion on the outer peripheral surface of the end of the winding core, the flange member has a concave portion into which the end of the winding core is inserted, and the end of the winding core is inserted into the concave portion, the projection having the winding core is in contact with the flange member, and the winding core is in contact with the flange member. and the flange member may be fixed.

Moreover, a fixing method other than the method of using a projection part may be sufficient. For example, the winding core and the flange member may be bonded and fixed with an adhesive. Further, the winding core and the flange member may be screwed.

The granules of the present invention may be enclosed in a package. A bag may be sufficient, and the container containing the container body which has an opening, and the lid|cover which closes the opening may be sufficient.

The material constituting the package is not particularly limited, and examples thereof include resins, and more specifically, polyolefin resins, polyethylene resins, and polypropylene resins.

The color tone of the package is not particularly limited, and examples thereof include transparent color, brown color, and black color. Especially, from the point of light resistance, brown or black is preferable and black is more preferable.

<Second sheet>

The granulated body of the present invention may be combined with a second sheet having a second layer containing a developer to form a sheet set for measuring pressure.

The second sheet may be handled as an assembly. That is, the sheet set for measuring pressure of the present invention is a first sheet having a first layer including a core, a pair of flange members fixed to both ends of the core, and microcapsules containing a color developer wound around the core. Even if it is composed of a first assembly having a first assembly, a winding core, a pair of flange members fixed to both ends of the winding core, and a second assembly having a second sheet wound around the core and having a second layer containing a developer. do.

When the sheet set for pressure measurement is used, the first sheet and the second sheet are laminated so that the first layer in the first sheet and the second layer in the second sheet face each other. By pressurizing the resulting laminate, the microcapsules are broken in the pressed region, the color developing agent contained in the microcapsules comes out of the microcapsules, and a color development reaction proceeds between the microcapsules and the developer in the second layer. As a result, in the pressed region, color development proceeds.

The second sheet has a second layer containing a developer. Especially, it is preferable that a 2nd sheet|seat contains a support body and the 2nd layer arrange|positioned on the support body.

Hereinafter, each member will be described in detail.

(support)

A support body is a member for supporting a 2nd layer. In addition, in the case where handling is possible with the second layer itself, the second sheet need not have a support body.

The support body may have any shape of a sheet form and plate form.

As a support body, a resin base material and synthetic paper are mentioned, A resin base material is preferable. As an aspect of the resin base material, the aspect of the resin base material contained in the 1st sheet|seat mentioned above is mentioned.

Moreover, as a support body, the aspect of the laminated body of the resin base material and adhesive layer demonstrated with the 1st sheet|seat mentioned above is also mentioned. Preferred aspects of the resin substrate and the adhesion layer are as described above.

The support body in the first sheet and the support body in the second sheet may be the same or different.

Since the color development state after pressure measurement is easily visually recognized through the support body, it is preferable that the support body in a 2nd sheet|seat is transparent, 0 to 20 % of the haze of a support body is preferable, and 0 to 10 % is more preferable.

(2nd floor)

The second layer is a layer containing a developer.

A color developing agent is a compound which does not have a color developing function by itself, but has the property of developing a color by contacting a color developing agent. As a developer, an electron-accepting compound is preferable.

As a developer, an inorganic compound and an organic compound are mentioned, Paragraph 0055 of international publication 2009/008248 - the inorganic compound and organic compound of 0056 are preferable. Acid clay, activated clay, or a metal salt of an aromatic carboxylic acid is preferable from the viewpoints of more excellent color development density and image quality after color development.

Although the content of the developer in the second layer is not particularly limited, it is preferably 20 to 95 mass%, more preferably 30 to 90 mass%, based on the total mass of the second layer, from the viewpoint of a more excellent color development density. .

Although content in particular of the developer in a 2nd layer is not restrict|limited, 0.1-30 g/m< ² > is preferable. When a developer is an inorganic compound, 3-20 g/m< ² > is preferable and, as for content of a developer, 5-15 g/m< ² > is more preferable. When a developer is an organic compound, 0.1-5 g/m< ² > is preferable and, as for content of a developer, 0.2-3 g/m< ² > is more preferable.

The second layer may contain components other than the above-mentioned developer.

Other components include, for example, polymer binders, pigments, optical brighteners, defoamers, penetrants, ultraviolet absorbers, surfactants, and preservatives.

Examples of the polymer binder include styrene-butadiene copolymer, polyvinyl acetate, polyacrylic acid ester, polyvinyl alcohol, polyacrylic acid, maleic anhydride-styrene copolymer, olefin resin, modified acrylic acid ester copolymer, starch, casein. , synthetic polymers and natural polymers such as gum arabic, gelatin, carboxymethyl cellulose or a salt thereof, and methyl cellulose.

As a pigment, ground calcium carbonate, light calcium carbonate, a talc, titanium dioxide, etc. are mentioned, for example.

Although the thickness in particular of a 2nd layer is not restrict|limited, From the point which the effect of this invention is more excellent, 1-50 micrometers is preferable and 2-30 micrometers is more preferable.

In addition, although the mass (g/m2) in particular of a ^2nd layer is not restrict|limited, From the point which the effect of this invention is more excellent, ^0.5-30 g/m2 is preferable.

(Method of forming the second layer)

The formation method in particular of the said 2nd layer is not restrict|limited.

For example, the method of apply|coating the composition for 2nd layer formation containing a developer on a support body, and drying the obtained coating film as needed is mentioned.

The composition for forming a second layer may be a dispersion in which a developer is dispersed in water or the like. A dispersion in which the developer is dispersed can be prepared by mechanically dispersing the inorganic compound in water when the developer is an inorganic compound. When the developer is an organic compound, it can be prepared by mechanically dispersing the organic compound in water or dissolving it in an organic solvent.

The other component which may be contained in the 2nd layer mentioned above may be contained in the composition for 2nd layer formation.

The method in particular of apply|coating the composition for 2nd layer formation is not restrict|limited, The method of using the coating machine used when apply|coating the composition for 1st layer formation mentioned above is mentioned.

After apply|coating the composition for 2nd layer formation on a support body, you may dry-process with respect to a coating film as needed. Heat processing is mentioned as a drying process.

In addition, although the method of forming a 2nd layer on a support body was described above, it is not limited to the said aspect, For example, after forming a 2nd layer on a temporary support body, peeling a temporary support body, and the 2nd You may form the 2nd sheet|seat which consists of layers.

As a temporary support body, if it is a peelable support body, it will not restrict|limit especially.

(other absence)

The second sheet may have members other than the support and the second layer described above.

For example, the 2nd sheet|seat may have the adhesive layer for improving the adhesiveness of both between a support body and a 2nd layer.

As for the aspect of the adhesion layer, the aspect of the adhesion layer which the above-mentioned 1st sheet|seat may have is mentioned.

As described above, in the first sheet and the second sheet, the first sheet and the second sheet are laminated so that the first layer of the first sheet and the second layer of the second sheet face each other to obtain a laminate, It is used by pressing against the laminate.

That is, the first sheet corresponds to a sheet used for measuring the pressure together with the second sheet.

The arithmetic mean roughness (Ra) of the second sheet is preferably 1.2 µm or less from the viewpoint of more excellent color development density. In addition, the arithmetic mean roughness Ra of the second sheet is intended to mean the arithmetic mean roughness Ra of the surface of the second sheet on the side opposite (contacting side) to the first sheet when the sheet set for pressure measurement is used. do. When the second layer is located on the outermost surface of the second sheet on the side opposite to the first sheet, the arithmetic mean roughness (Ra) is the arithmetic mean roughness (Ra) of the surface opposite to the support side of the second layer corresponds to

Example

The present invention will be described in more detail below based on Examples. Materials, usage amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the Examples shown below. In addition, in the following, unless otherwise indicated, "part" and "%" are based on mass.

<Example 1>

After biaxial stretching, the 75-micrometer-thick long polyethylene terephthalate film (PET film) (450 mm in width) which both surfaces performed corona discharge treatment was prepared. Next, on one surface of the obtained PET film, the composition A for adhesive layer formation mentioned later was apply|coated and dried with a bar coater, and the adhesive layer A of 0.45 micrometer thickness was formed.

The composition of the composition A for adhesive layer formation is as follows.

In addition, the mass of each dispersion liquid when the total mass of the composition was 100 mass parts was expressed as "mass part".

-Composition A- for forming an adhesive layer

・Styrene/butadiene copolymer latex (styrene: butadiene = 67: 30, product name: LX-407C5, manufactured by Nippon Zeon Co., Ltd., solid content 40% by mass) 14.1 parts by mass

-2,4-dichloro-6-hydroxy-s-triazine (solid content 8 mass %) 2.5 parts by mass

Polystyrene particles (product name: UFN1008, manufactured by Nippon Zeon Co., Ltd., average particle: 2 µm, solid content 20 mass%) 0.04 parts by mass

·Distilled water 83.4 parts by mass

Then, the composition B for forming an adhesion layer comprising the following composition was applied and dried on the adhesion layer A by a bar coater to form a 0.1 µm adhesion layer B, and a support body 1 was obtained.

-Composition B- for forming an adhesive layer

· 10.4% aqueous solution of gelatin (761 gelatin, manufactured by Nitta Gelatin Co., Ltd., solid content 100%) 10 copies

3.5% methanol solution of 1,2-benzothiazolin-3-one 0.04 parts

- 3% aqueous solution of hydroxypropylmethylcellulose (Metroz TC5R, manufactured by Shin-Etsu Chemical Co., Ltd., solid content 100%) 0.67 parts

・A 1% aqueous solution of sodium hydroxide (Naroacti CL-95: manufactured by Sanyo Chemical Industry Co., Ltd., solid content 1%) 0.7 parts

Antimony dope tin oxide dispersion (TDL-S: manufactured by Mitsubishi Materials Co., Ltd., solid content 17%, inorganic particles having antistatic properties) 4.9 parts

·Distilled water 83.7 parts

3,3-bis(2-methyl-1-octyl-3-indolyl)phthalide (18 parts by mass) was dissolved in diarylethane (70 parts by mass) as a color developer to obtain a solution A. Furthermore, the butylene oxide adduct (0.4 mass part) of ethylenediamine melt|dissolved in methyl ethyl ketone (1 mass part) was added to the stirring solution A, and the solution B was obtained. Furthermore, the trimethylolpropane adduct (2 mass parts) of tolylene diisocyanate melt|dissolved in methyl ethyl ketone (1 mass part) was added to the stirring solution B, and the solution C was obtained.

Next, the said solution C was added in the solution which melt|dissolved polyvinyl alcohol (6 mass parts) in water (150 mass parts), and it emulsified and dispersed. Water (300 parts by mass) was added to the emulsion after emulsification and dispersion, heated to 70° C. while stirring, and cooled after stirring for 1 hour to prepare a microcapsule solution containing microcapsules containing a color developer. The average particle diameter of the obtained microcapsules was 20 m. The prepared microcapsule solution was used as a color-developing agent-encapsulated microcapsule solution (A).

Water (75 parts by mass), sodium polyacrylate (5 parts by mass) and calcium carbonate (100 parts by mass) were mixed and dispersed in a sand mill, followed by SBR latex (equivalent to 15 parts by mass of solid content), and 1% by mass of carboxymethylcellulose aqueous solution ( 15 mass parts) and 25 mass % sodium dodecylbenzenesulfonate aqueous solution (1 mass part) were added and mixed, water was added again, the solid content concentration was 41.5 mass %, and the composition for protective double layer formation was manufactured. .

Next, on the adhesion layer B of the support body 1, two protective layers are formed at both ends in the width direction of the support body 1, and a first layer is formed between the protective two layers. On the surface on the layer B side, the color developer-encapsulated microcapsule liquid (A) was applied, and then the composition for forming a protective double layer was applied so as to be in contact with both ends in the width direction, and then dried to obtain a sheet. Among the obtained sheets, the width of the first layer was 400 mm and the width of the protective double layer was 25 mm on one side (50 mm on both sides).

Then, the central portion of the sheet was cut to a width of 360 mm using a processing machine to remove the protective double layers located at both ends in the width direction of the obtained sheet, and a long article having a support body 1 and a first layer disposed on the support body 1 . 1 sheet was obtained. On the obtained first sheet, the following double-sided tape is attached to both ends in the width direction, the following cushion (spacer) is attached, and as shown in Figs. was prepared.

Next, the hollow cylindrical winding core mentioned later and the flange member mentioned later were prepared. Further, the flange member has a substrate and a cylindrical insertion portion disposed on the substrate, and a projection portion is disposed on the surface of the insertion portion (see Figs. 2 and 3). The insertion part of the flange member was inserted into the hollow part of the core, and the flange member was fixed to both ends of the core, and the core with a flange member was manufactured.

Next, the first sheet on which the spacer was disposed was wound around the core of the winding core provided with the flange member to prepare the granulated body 1 shown in Fig. 1 having a cross-sectional diameter at both ends (outer diameter of the roll of the first sheet) of 170 mm. .

-Spacer-

Material: Neoprene foam rubber (manufactured by Tokiwa Rubber Co., Ltd.), Width: 15 mm, Thickness: 5 mm, Static friction coefficient: 0.63, Dynamic friction coefficient: 0.62

-Double-sided tape-

Paper + Acrylic adhesive (Sekisui Chemical Industry Co., Ltd., Double tack tape #595), Width: 10 mm

-Kwon Shim-

Paper (resin impregnated), length: 390 mm, hollow inner diameter: 76 mm

-Flange member (see Fig. 2)-

Material: polypropylene (PP), substrate shape: octagonal, substrate size: 210 mm, diameter of circumscribed circle (diameter of circumscribed circle circumscribed in the region consisting of the insert and protrusions when the flange member is observed from the normal direction of the substrate) : 77.5 mm, number of protrusions: 8 equally spaced, protrusion height: 1.3 mm

<Examples 2 to 15, Comparative Example 1>

Granules 2 to 15 of Examples 2 to 15 and granules C1 of Comparative Example 1 were manufactured in the same manner as in Example 1, except that various requirements shown in Table 1 to be described later were changed.

In addition, the supports 2-14 described in a table|surface were manufactured with the following method.

(Preparation of support 2)

Except for replacing the styrene/butadiene copolymer latex with a styrene-acrylic copolymer (AS-563A, manufactured by Daicel Finecam Co., Ltd., solid content 27.5 mass%), in the same manner as in the composition A for forming the adhesion layer, for forming the adhesion layer Composition C was prepared.

The composition A for adhesion layer formation was changed into the composition C for adhesion layer formation, and except having changed thickness, it carried out similarly to the support body 1, and obtained the support body 2.

(Preparation of supports 3 and 5 to 14)

Except having changed the various requirements shown in Table 1 mentioned later, it carried out similarly to the support body 1, and obtained the supports 3, 5-14.

(Preparation of support 4)

The composition C for adhesive layer formation was apply|coated on both surfaces of the 75-micrometer-thick long polyethylene terephthalate film (PET film) uniaxially stretched in the longitudinal direction, and it dried. Next, it extended|stretched in the width direction, heat-setting and heat relaxation were carried out, and the support body 4 was obtained.

<Production of the second sheet>

Activated clay (BYK-chemie, FURACOLOR SR) (100 parts by mass), Na hexametaphosphate (Nippon Chemical Industry, sodium hexametaphosphate) (0.5 parts by mass), 10% aqueous sodium hydroxide solution (15 parts by mass), and water (240 parts by mass) was added, and to the obtained dispersion, an olefin resin (Arakawa Chemical Industry, Polymalon 482) (30 parts by mass), a modified acrylic acid ester copolymer (Nippon Zeon, Nippol LX814) (35 parts by mass), carboxy 1% aqueous solution (80 parts by mass) of sodium methylcellulose (Daichi Kogyo Pharmaceutical Co., Ltd., Cellogen EP), 15% aqueous solution (18 parts by mass) of Na alkylbenzenesulfonate (Daichi Kogyo Pharmaceutical Co., Ltd., Neogen T), polyoxyethylene 1% aqueous solution (20 parts by mass) of polyoxypropylene lauryl ether (Daichi Kogyo Pharmaceutical Co., Ltd., Neugen LP-70), sodium-bis(3,3,4,4,5,5,6,6,6- A 1% aqueous solution (20 parts by mass) of nonafluorohexyl)-2-sulfinate oxysuccinate (FUJIFILM, W-AHE) was mixed to obtain a composition for forming a second layer containing a clay substance.

The composition for forming the second layer was applied on the support 1 so that the solid content application amount was 7 g/m ² . Next, the obtained coating film was dried, the 2nd layer was formed, and the 2nd sheet|seat was obtained. In addition, the haze of the support body 1 was 10 % or less.

<Measurement>

(burglar)

From the first sheet produced in each Example and Comparative Example, a test piece of 200 mm in the longitudinal direction (vertical direction) and 15 mm in the width direction (horizontal direction) was cut out, using a LOOP STIFFNESS TESTER (manufactured by Toyo Seiki Seisakusho), The strength of the first sheet in the longitudinal direction and in the width direction was measured. Measurement conditions were a clamp interval distance of 100 mm, a loop length of 85 mm, and a compression rate of 3.3 mm/sec. The above measurement was performed on two test pieces, the average value of the strength in the longitudinal direction obtained from the two test pieces was taken as the strength in the longitudinal direction of the first sheet, and the average value of the strength in the width direction obtained from the two test pieces was taken as the first It was set as the intensity|strength in the width direction of a sheet|seat. In addition, when measuring the strength in the longitudinal direction of the first sheet, a test piece cut out so that the longitudinal direction of the test piece follows the longitudinal direction of the first sheet is used, and when measuring the strength in the width direction of the first sheet, the strength of the test piece is The test piece cut out so that the longitudinal direction might follow the width direction of the 1st sheet|seat was used.

<Evaluation>

(drop test)

Based on the distribution condition level I of JIS Z0202, each granulated body was dropped by one corner, three corners, and six surfaces, and the following reference|standard evaluated. A result is shown in Table 1.

A: No trace of destruction of the microcapsule was confirmed.

B: Traces of breakage of microcapsules were recognized slightly (actual usable level).

C: Many traces of destruction of the microcapsule were recognized.

(color granularity)

The first sheet included in each assembly and the second sheet cut to a size of 5 cm in length × 5 cm in width are overlapped with the surface of the first layer of the first sheet and the surface of the second layer of the second sheet facing each other did. Both the overlapping sheets were sandwiched between two glass plates with a smooth surface, placed on a desk, and a weight was placed on the glass plate to pressurize it at a pressure of 0.2 MPa to develop color. Thereafter, the shape of the color development surface of the second sheet developed was visually observed from the support (PET sheet) side through the support, and evaluated according to the following evaluation criteria. In addition, the sample of Comparative Example 1 was not evaluated because the capsule was broken in the drop test. Table 1 shows the evaluation results.

A: The graininess in the color development surface is very small.

B: There is a slight graininess on the color development surface, but there is no problem in practical use.

C: The graininess in the color development surface is clearly large.

As shown in Table 1, when the granules of the present invention were used, desired effects were obtained.

Especially, from the comparison of Example 4 with another Example, when the thickness of a spacer was 2.5 micrometers or more, it was confirmed that the more excellent effect was acquired.

Further, from a comparison of Examples 8, 10 and 15 with other examples, it was confirmed that a more excellent effect was obtained when the strength in the width direction (transverse direction) of the first sheet was 165 mN or more.

Moreover, from the comparison of Examples 10 and 15 with another Example, when the intensity|strength in the width direction/strength in the longitudinal direction was 1.00 or more, it was confirmed that the more excellent effect is acquired.

Moreover, from the comparison of Example 12 with another Example, when the thickness of an adhesive layer was 2.0 micrometers or less, it was confirmed that the effect more excellent in color development granularity is acquired.

Moreover, from the comparison of Example 14 with another Example, when there was an adhesive layer, it was confirmed that the more excellent effect was acquired, and that it was excellent in color development granularity.

<Example 16>

Synthetic isoparaffin (Idemitsu Kogsan Co., Ltd., IP solvent 1620) (15 parts by mass), N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine dissolved in ethyl acetate (3 parts by mass) (Adeca Co., Ltd., Adeca polyether EDP-300) (0.4 parts by mass) was stirred, 1-phenyl-1-xylylethane (Shin-Nippon Petroleum Co., Ltd., Hysol SAS296) (78 parts by mass) ) to obtain a solution D.

Further, a trimethylolpropane adduct (DIC Corporation, Vernock D-750) (3 parts by mass) of tolylene diisocyanate dissolved in ethyl acetate (7 parts by mass) was added to the stirred solution D to obtain a solution E. .

And said solution E was added in the solution which melt|dissolved polyvinyl alcohol (PVA-205, Kuraray Corporation) (69 mass parts) in water (140 mass parts), and it emulsified and dispersed. Water (340 parts by mass) was added to the emulsion after emulsion dispersion, and it heated to 70 degreeC while stirring, and cooled after stirring for 1 hour. Further, water was added to adjust the concentration to obtain a color developer non-encapsulating microcapsule liquid (B) having a solid content concentration of 19.6%.

The above-obtained color-developer-encapsulated microcapsule liquid (A) (18 parts by mass), non-color-developer-encapsulated microcapsule liquid (B) (2 parts by mass), water (63 parts by mass), carboxymethylcellulose Na (Daichi Kogyo Pharmaceutical Co., Ltd.) ), a 10% aqueous solution (1.8 parts by mass) of cellogen 5A), a 1% aqueous solution (30 parts by mass) of carboxymethylcellulose Na (Daichi Kogyo Pharmaceutical Co., Ltd., Cellogen EP), sodium alkylbenzenesulfonate (Daichi) A 15% aqueous solution (0.3 parts by mass) of Kogyo Pharmaceutical Co., Ltd., Neogen T) and a 1% aqueous solution (0.8 parts by mass) of Neugen LP70 (Daichi Kogyo Pharmaceutical Co., Ltd.) are mixed, and stirred for 2 hours By doing so, a specific composition was obtained.

Assembly 16 was prepared according to the same procedure as in Example 1, except that the specific composition was used instead of the color developer-encapsulated microcapsule liquid (A) and the PET film used was changed.

<Examples 17 to 22, Comparative Example 2>

Granules 17 to 22 of Examples 17 to 22 and granules C2 of Comparative Example 2 were manufactured according to the same procedure as in Example 16 except that various requirements shown in Table 2 to be described later were changed.

The above-mentioned measurement and evaluation were performed using the granules 16-22 and granule C2 obtained above. A result is put together in Table 2, and is shown.

In addition, in the evaluation of the color development granularity in Examples 16-22, the pressure was changed to 0.05 MPa, and it evaluated. The sample of Comparative Example 2 was not evaluated for color granularity because the capsule was broken in the drop test.

As shown in Table 2, when the granules of the present invention were used, desired effects were obtained.

Moreover, from the comparison of Examples 16-22, when the intensity|strength of the width direction was 175 mN or more, it was confirmed that the more excellent effect is acquired.

Moreover, from the comparison of Example 22 with another Example, when there was an adhesive layer, it was confirmed that the more excellent effect was acquired, and it was excellent in color development granularity.

10: assembly
12 : heart
14: Flange member
16: roll of the first sheet
18: substrate
20: insertion part
22: protrusion
24: first sheet
26: resin base
28: adhesion layer
30: 1st floor
32: spacer
34: microcapsule

Claims (13)

heart and mind,
A granulated body having a roll of the first sheet formed by winding a long first sheet around the core,
the first sheet has a long resin substrate and a first layer comprising microcapsules containing a color developer disposed on the resin substrate;
and the strength in the width direction of the first sheet is 150 mN or more. The method of claim 1,
and a strength in a width direction of the first sheet is greater than a strength in a length direction of the first sheet. 3. The method of claim 2,
wherein the strength in the longitudinal direction of the first sheet is 180 mN or less. 4. The method according to any one of claims 1 to 3,
and the strength in the width direction of the first sheet is at least 165 mN. 5. The method according to any one of claims 1 to 4,
and a pair of spacers disposed between the first sheets of the roll of the first sheet and spaced apart from each other in the width direction of the first sheet. 6. The method of claim 5,
The spacer has a thickness of 1-5 mm. 7. The method according to any one of claims 1 to 6,
and the first sheet further has an adhesive layer between the resin substrate and the first layer. 8. The method of claim 7,
The granulated body, wherein the adhesive layer contains a resin having a repeating unit derived from styrene or a derivative thereof. 9. The method according to claim 7 or 8,
The thickness of the adhesive layer is 0.01 to 2.0 ㎛, granules. 10. The method according to any one of claims 1 to 9,
The assembly further having a pair of flange members fixed to both ends of the winding core. The assembly according to any one of claims 1 to 10, and
A sheet set for pressure measurement having a second sheet having a second layer comprising a developer. A first sheet having an elongated resin substrate and a first layer comprising microcapsules containing a coloring agent disposed on the resin substrate;
A sheet set for pressure measurement comprising a second sheet having a second layer comprising a developer, the sheet set comprising:
The sheet set for pressure measurement, wherein the strength of the first sheet in the width direction is 150 mN or more. A sheet having an elongated resin substrate and a first layer comprising microcapsules containing a coloring agent disposed on the resin substrate, the sheet comprising:
The sheet, wherein the first sheet has a strength in the width direction of 150 mN or more.

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