JP2013155121A - Elongatable organic base material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an elongatable organic base material that is elongatable, has a part hardly suffering from shape changes when elongated and exhibits excellent weather resistance.SOLUTION: An elongatable organic base material comprises an elongatable matrix and, partially and integrally formed therein, a hardly elongatable part, where the elongatable matrix contains a weather-resistant agent. As the weather-resistant agent, at least one selected from among ultraviolet absorbers and antioxidants can be used. The hardly elongatable part can be partially formed in the elongatable matrix in such a state that it is exposed or unexposed on at least one surface of the elongatable organic base material.

Description

  The present invention relates to an extensible organic base material having a difficult extension portion. The extensible organic base material can be used as, for example, a band member, a binding member, a sanitary article, a clothing part, a base cloth for a poultice, etc. by utilizing its extensibility and stretchability. In addition, when the stretchable organic base material is stretched, the whole base material is stretched, but the difficult stretch portion is not stretched and its shape is maintained. Therefore, a design such as a character is applied to the difficult stretch portion. Or other members can be held and fixed. For this reason, for example, it can utilize also for an electronics member, an optical member, an optoelectronic member, a car electronics member, a member for household appliances, a member for housing equipment, a building material, etc. Moreover, since it has weather resistance, it is hard to deteriorate outdoors and can be used for a long time.

  Organic members having extensibility and stretchability are widely used for band members, binding members, sanitary products, clothing items, poultice base fabrics, and the like. The extensible member is usually composed of a composition having uniform extensibility (Patent Document 1). However, when such an extensible member is extended, every part of the extensible member is extended. Further, in a member having not only extensibility but also elasticity, when this is expanded and contracted, all parts expand and contract. Therefore, even if a design is applied to a certain place, the design is distorted when the extensible member is extended. Moreover, when fixing another member to an extensible member, since every part of an extensible member expand | extends, it is difficult to hold | maintain and fix this other member reliably.

JP 2003-342169 A

Accordingly, an object of the present invention is to provide an extensible organic base material that has extensibility, has a portion whose shape does not easily change even when extended, and is excellent in weather resistance.
Another object of the present invention is to provide an extensible base material that has stretchability in addition to extensibility, has a portion whose shape does not easily change even when stretched, and is excellent in weather resistance.

  As a result of intensive studies to achieve the above object, the present inventors can solve the above-mentioned problems by partially and integrally forming a difficultly stretched part in an extensible base material containing a weathering agent. The present invention has been completed.

  That is, the present invention is an extensible organic base material in which a difficultly stretchable part is partially and integrally formed in an extensible base material, wherein the extensible base material contains a weathering agent. An organic base material is provided.

  As said weathering agent, at least 1 sort (s) chosen from a ultraviolet absorber and antioxidant can be used.

  In the extensible organic base material, the hardly extensible portion may be partially formed in the extensible base material with or without being exposed on at least one surface of the extensible organic base material. .

  The surface shape of the hardly elongated portion, or the projected shape when the surface of the extensible organic base material of the difficultly elongated portion is a projection surface is a substantially circular shape, a substantially polygonal shape, an amorphous shape, or a shape representing a character, symbol or number, It may be either ring-shaped or linear.

  The length of the long axis in the surface direction of the difficult extension portion is, for example, 0.05 mm to 10 cm.

  A plurality of difficultly elongated portions may be formed in a regular pattern in the extensible base material. In this case, the distance between adjacent difficult extension parts is, for example, 0.05 mm to 50 cm.

  The thickness of the extensible organic substrate is, for example, 0.01 mm to 1 cm.

  The length in the thickness direction of the difficultly stretched portion is preferably at least 1/50 of the thickness of the extensible organic base material. Moreover, the said difficult extension part may be continuously formed from one surface of the extensible organic base material to the other surface. Further, the elongation characteristic may have a gradation in the vicinity of the interface between the hardly elongated portion and the extensible base material.

  The extensible organic base material may further have stretchability.

According to the extensible organic base material of the present invention, even if the base material is stretched in one direction, the shape of the hardly stretchable portion hardly changes, so that the shape does not change while having a function as a stretchable member. A desired design can be given to the part, and other members can be held and fixed. Moreover, since the extensible base material contains a weathering agent, it is difficult to deteriorate even when used outdoors, and can be used outdoors for a long time.
In addition, according to the stretchable organic base material having further stretchability, the shape of the hardly stretchable polymer portion hardly changes even when the base material is stretched, while having the function as a stretchable member. It becomes possible to give a desired design to the shape-invariant portion and hold and fix other members. In addition, since the extensible base material contains a weathering agent, it is hardly deteriorated even when used outdoors, and can be used outdoors for a long time.

It is a schematic perspective view which shows an example of the extensible organic base material of this invention. It is a schematic perspective view which shows the II-II sectional view of the extensible organic base material of FIG. It is the schematic (sectional drawing) which shows an example of the manufacturing method of the extensible organic base material of this invention. It is the schematic (sectional drawing) which shows the other example of the manufacturing method of the extensible organic base material of this invention. It is the schematic (sectional drawing) which shows the other example of the manufacturing method of the extensible organic base material of this invention. It is a figure (top view) which shows the example of the test sample of the extensible organic base material used with a tension test and a hysteresis test.

[Extensible organic substrate]
The extensible organic base material of the present invention is an organic base material in which a hardly extensible portion is partially and integrally formed in an extensible base material containing a weathering agent. When the extensible organic base material of the present invention is stretched in one direction (plane direction), the stretchable base material portion is stretched, but the partially formed difficult stretch portion is not stretched or hardly stretched. For this reason, the design in which a shape is desired not to change can be given to a difficult expansion | extension part, or another member can be fixed and hold | maintained. Moreover, since this extensible organic base material contains a weathering agent, it can be used for a long time outdoors.

  FIG. 1 is a schematic cross-sectional view showing an example of the extensible organic base material of the present invention. FIG. 2 is a schematic perspective view showing a II-II cross section of the extensible organic substrate of FIG. 1 and 2, a sheet-like extensible organic base material 1 is formed partially and integrally with an extensible base material 2 (extensible base material portion) and the extensible base material 2. It is comprised with the difficult expansion | extension part 3. FIG.

  The difficultly stretchable portion 3 may be formed partially and integrally in the extensible base material 2, for example, may be formed only at one location, and may be scattered or scattered in a plurality of locations discontinuously. You may do it.

  The shape of the difficultly extending portion 3 is not particularly limited, and can be appropriately selected according to the purpose. Shape), indefinite shape, and the like. Moreover, as the difficult extension part 3, (i) Projection shape when the surface shape of this difficulty extension part 3 or the extensible organic base material surface of this difficulty extension part 3 is used as a projection surface (namely, said extension organic group) The shape viewed from the surface side of the material; hereinafter referred to as “substrate surface projected shape”) is generally circular, substantially polygonal (approximately triangular, approximately rectangular, approximately pentagonal, approximately hexagonal, etc.), amorphous, Or a solid column-shaped difficultly stretched portion that represents a character, symbol, or number (the entire inside is filled with the hardly stretchable material from the boundary with the stretchable base material), (ii) the difficultly stretched portion (3) a hard-to-extend portion of a cylindrical shape (hollow column shape) whose surface shape or substrate surface projection shape is an annular shape (annular) (the region corresponding to the cylindrical hollow portion is made of an extensible material); It may be any of the difficultly stretched part 3 in which the surface shape of the difficultly stretched part 3 or the projected shape of the substrate surface is linear. Moreover, the difficult extension part of these shapes may be mixed.

  When the difficult extension part 3 is a cylindrical difficult extension part whose surface shape or substrate surface projection shape is an annular shape (annular), the region corresponding to the cylindrical cavity of the cylindrical difficult extension part is extensible. Since it is made of a material, it can be stretched or stretched in the thickness direction, and is excellent in wearability on an uneven adherend. In the region made of an easily stretchable material that hits the cylindrical hollow portion of the tubular difficult extension portion, one or more difficult extension portions (i), (ii), or (iii) are further formed. May be.

  Moreover, when the said difficult extension part 3 is a difficult extension part in which the surface shape or base-material surface projection shape becomes linear, the extension extension (extension | restoration of an extension | extension) is carried out by this difficult extension part 3. It is possible to provide strength in a specific direction.

  In the present invention, when the difficult extension part 3 is a solid columnar difficult extension part extending in the sheet thickness direction, the length (for example, diameter) of the long axis (longest part) in the surface direction of the difficult extension part is, for example, 0. .05 mm to 10 cm. When this length is too small, the utility value of a difficult extension part will become small, and on the contrary, it will become difficult to manufacture. Further, for example, when a plurality of difficultly extending portions 3 are formed and the distance (shortest distance) between adjacent difficultly extending portions is, for example, 0.05 mm to 50 cm, the long axis in the surface direction of the difficultly extending portion (longest length) If the length of the part is less than 0.05 mm, the technical significance of having a shape-invariant site is reduced even when the entire extensible organic base material is extended in one direction. Moreover, when this length exceeds 10 cm, not only manufacture becomes difficult, but the said technical significance tends to become small. In this case, the length of the long axis (longest portion) in the surface direction of the difficultly stretched portion is preferably 0.1 mm or more, more preferably 0.5 mm or more, further preferably 1 mm or more, and particularly preferably 2 mm or more, In particular, 5 mm or more is preferable. Moreover, 8 cm is preferable and, as for the upper limit of the length (longest part) of the long axis of the surface direction of a difficult extension part, 5 cm is especially preferable.

  In the present invention, when the difficult extension part 3 is a cylindrical difficult extension part whose surface shape or substrate surface projection shape is an annular shape (annular), the shape of the annular zone (ring) (the outer peripheral shape and / or the inner shape) The peripheral shape, particularly the outer peripheral shape, is not particularly limited, and can be appropriately selected according to the purpose. ), Amorphous (indefinite), or a shape representing a character, symbol or number; a known figure, a shape representing a mark, or the like. In the case where the surface shape or the substrate surface projection shape of the cylindrical difficulty extending portion is substantially polygonal, the inner angle may be 90 degrees or less, or may be an angle exceeding 90 degrees. From the viewpoint of ease of manufacture, the surface shape or the projected surface of the base material (outer peripheral shape and / or inner peripheral shape, particularly the outer peripheral shape) of the cylindrical difficulty extending portion is preferably substantially circular or rectangular. Moreover, the length (for example, diameter) of the long axis (longest part of the shape which makes | forms an outer periphery) of the surface direction of a cylindrical difficulty expansion | extension part is 0.05 mm-10 cm, for example. When this length is too small, the utility value of a cylindrical difficulty extension part will become small, and on the contrary, it will become difficult to manufacture. For example, when a plurality of cylindrical difficult extension parts are formed and the distance (shortest distance) between adjacent cylindrical difficulty extension parts is 0.05 mm to 50 cm, for example, the surface direction of the cylindrical difficult extension parts If the length of the long axis (the longest part of the shape forming the outer periphery) is less than 0.05 mm, the technical significance of having a shape-invariant portion is reduced even when the entire extensible organic base material is extended in one direction. Moreover, when this length exceeds 10 cm, not only manufacture becomes difficult, but the said technical significance tends to become small. The length of the long axis in the surface direction of the cylindrical difficult-to-extend part (the longest part of the shape forming the outer periphery) is preferably 0.1 mm or more, more preferably 0.5 mm or more, still more preferably 1 mm or more, and particularly preferably 2 mm. Above, especially 5 mm or more is preferable. In addition, the upper limit of the length of the long axis in the surface direction of the cylindrical difficulty extending portion (the longest portion of the shape forming the outer periphery) is preferably 8 cm, and particularly preferably 5 cm.

  The width of the annular zone (that is, the distance between the outer peripheral surface and the inner peripheral surface of the cylindrical difficult extension part; the thickness) which is the surface shape of the cylindrical difficult extension part or the projected surface of the substrate is appropriately determined according to the purpose. Although it can be selected, it is usually 1 to 40% of the length of the long axis (the longest part of the shape forming the outer periphery) in the surface direction of the cylindrical difficult-to-extend part. The lower limit of the width of the annular zone (thickness of the cylindrical difficult extension portion) is preferably 2% with respect to the length of the long axis (the longest part of the shape forming the outer periphery) in the surface direction of the cylindrical difficult extension portion. More preferably, it is 5%. Further, the upper limit of the width of the annular zone (thickness of the cylindrical difficult extension portion) is preferably relative to the length of the long axis in the surface direction of the cylindrical difficult extension portion (longest portion of the shape forming the outer periphery). 30%, more preferably 20%. More specifically, the width of the annular zone (thickness of the difficult-to-extend cylindrical portion) is, for example, 0.01 mm to 4 cm, and the lower limit thereof is preferably 0.02 mm, more preferably 0.1 mm. More preferably, it is 0.2 mm, particularly preferably 0.4 mm, especially 1 mm, and the upper limit is preferably 3 cm, more preferably 2 cm.

  In the present invention, in the case where the surface shape of the difficultly elongated portion 3 or the substrate surface projection shape is a linear shape, the type of the linear shape is not particularly limited, and for example, a linear shape, a broken line shape, a wavy line shape, or an arc line It may be a curved line such as a shape or an amorphous line. In addition, when the sheet-like organic base material 1 having extensibility has a plurality of hardly extensible polymer portions in which the surface shape or the substrate surface projection shape is linear, the plurality of hardly extensible polymer portions are They may be parallel, crossed, or in a twisted position. The line width (line width) which is the surface shape of the difficultly elongated portion 3 or the substrate surface projected shape can be appropriately set according to the purpose and application, and is, for example, 0.01 mm to 5 cm. The lower limit of the line width (line width) which is the surface shape of the difficultly elongated portion 3 or the substrate surface projection shape is preferably 0.05 mm, more preferably 0.1 mm. The upper limit of the line width (line width) which is the surface shape of the difficultly elongated portion 3 or the substrate surface projected shape is preferably 2 cm, more preferably 1 cm. The length of the line that is the surface shape of the difficultly elongated portion 3 or the projected surface shape of the base material can be appropriately set according to the purpose and application, and is, for example, 0.5 mm to 10 m. The lower limit of the length of the line that is the surface shape of the difficultly elongated portion 3 or the projected shape of the substrate surface is preferably 5 mm, more preferably 1 cm. The upper limit of the length of the line that is the surface shape of the difficultly elongated portion 3 or the projected shape of the substrate surface is preferably 5 m, and more preferably 1 m. The ratio of the line length to the line width (line length / line width) which is the surface shape of the difficultly elongated portion 3 or the substrate surface projection shape (line length / line width) is, for example, 3 or more, preferably 5 or more, more preferably 10 or more. More preferably, it is 50 or more, and particularly preferably 100 or more.

  In the vicinity of the interface (boundary part) between the difficultly stretchable part 3 and the stretchable base material part 2, a gradation (gradient) in which the composition and / or physical properties (elongation characteristics, hardness, etc.) gradually change may be formed. An extensible organic base material having such a gradation (for example, a gradation about the elongation rate described later) in the vicinity of the interface between the hardly extensible portion 3 and the easily extensible base material portion 2 extends, for example, the extensible organic base material. When it is, it has the characteristic that it is hard to cut | disconnect at the interface of the difficult extension part 3 and the extensible base material part 2. FIG. Further, not only the vicinity of the interface (boundary part) between the difficultly stretchable part 3 and the extensible base material part 2 but also the many parts or the whole of the difficult stretchable part 3 and / or the extensible base material part 2 exhibit gradation. May be. In the extensible organic base material having a gradation portion, the boundary between the difficult extension portion 3 and the extensible base material portion 2 is the hardness of the non-gradient portion of the extensible base material portion 2 [over the entire extensible base material portion. When the gradation is exhibited, the hardness of the lowest hardness portion and the hardness of the non-gradient portion of the difficult extension portion 3 [when the gradation is exhibited over the entire difficult extension portion 3, the hardness is the highest. It can be determined by a line connecting the average value of the hardness of the high part].

  In the present invention, the difficultly stretchable part 3 may be formed in any part of the stretchable base material 2, but is formed in a state where it is exposed on at least one surface in that the difficultly stretchable part 3 can be effectively used. It is preferable. The difficult extension part 3 may be formed in the state which is not exposed to the surface of an extensible organic base material. The surface shape (at least one surface shape) of the difficultly stretchable part 3 or the projected shape when the surface of the extensible organic base material of the difficultly stretchable part 3 is a projection surface is substantially circular, substantially rectangular, indeterminate, or ring-shaped ( (Circular), linear, etc. may be sufficient. In addition, when the difficulty extending | stretching part 3 is a shape extended in a sheet | seat thickness direction, the cross-sectional shape of the difficulty extending | stretching part 3 is often the same as the surface shape in many cases. From the viewpoint of ease of manufacture, the surface shape of the difficultly elongated portion 3 is preferably substantially circular. Moreover, in order to ensure the smooth extensibility of the extensible organic base material, it is preferable that the hardly extensible portion 3 is formed at a place other than the end portion in the surface direction of the extensible base material 2. That is, it is preferable that the difficultly stretchable portion 3 is formed in a state of being included in the stretchable base material 2 (excluding both surfaces). However, when the end portion in the surface direction of the extensible base material 2 is reinforced, or when different properties are imparted to the end portion, the hardly stretchable portion 3 may be formed at the end portion.

  When a plurality of difficultly stretchable portions 3 are formed in the extensible base material 2, the plurality of difficultly stretchable portions 3 may be formed randomly or in a regular pattern. When the plurality of hardly extensible polymer portions 3 are formed in a regular pattern, the distance between the adjacent hardly extensible portions 3 (shortest distance) is, for example, 0.05 mm to 50 cm, and the upper limit of the distance is It is preferably 30 cm, more preferably 20 cm, still more preferably 15 cm, and particularly preferably 10 cm. The lower limit of the distance is preferably 0.1 mm, more preferably 1 mm, still more preferably 3 mm, and particularly preferably 5 mm. If the difficultly elongated portions 3 are formed in a regular pattern in advance, a large number of extensible organic substrates can be efficiently produced by cutting. In addition, when the plurality of difficult extending portions 3 are formed, the shapes and sizes of the plurality of difficult extending portions 3 may be the same or different. When the plurality of difficultly extending portions 3 have the same shape and size, an extensible organic base material having the same shape and size can be produced with high production efficiency.

  The thickness of the extensible organic substrate 1 of the present invention is, for example, 0.01 mm or more, preferably 0.03 mm or more, and more preferably 0.05 mm or more. The upper limit of the thickness of the extensible organic substrate 1 is, for example, 1 cm, preferably 5 mm, and more preferably 2 mm.

  The difficultly stretchable part 3 may be continuously formed from one surface of the extensible organic base material 1 and is continuously formed from one surface of the extensible organic base material 1 to the other surface. It may be. Further, the difficultly stretched portion 3 may be formed by being buried in the extensible organic base material 1. In any case, the length (thickness) in the thickness direction of the difficultly stretchable portion 3 is preferably at least 1/50, more preferably at least 1 of the thickness of the extensible organic substrate 1 in any of the above cases. / 20, more preferably at least 1/10, particularly preferably at least 1/4. In addition, from the viewpoint of retention of other members, for example, when the difficultly stretchable part 3 is continuously formed from one surface of the stretchable organic substrate 1, the thickness of the difficultly stretchable part 3 is determined. The length (thickness) in the direction is further preferably at least 1/3, particularly at least 1/2 (especially at least 2/3) of the thickness of the extensible organic substrate 1.

  The elongation (breaking elongation) of the stretchable organic substrate of the present invention in a tensile test (test specimen width 20 mm, chuck-to-chuck distance 50 mm, temperature 25 ° C., tensile speed 200 mm / min) is preferably 50% or more. It is preferably 70% or more, more preferably 120% or more, and the strength (breaking stress) is preferably 1.0 MPa or more, more preferably 2.0 MPa or more, and further preferably 3.0 MPa or more. The higher the strength, the better, but the upper limit is, for example, 100 MPa, and usually 50 MPa or less. An example of a test sample of an extensible organic base material used in a tensile test using a tensile tester is shown in FIG.

In the extensible organic base material of the present invention, the extensible base material 2 is excellent in extensibility, but the difficult extension portion 3 has low extensibility. When the stretchable organic substrate of the present invention is stretched to 1.5 times (150% of the original length) in an elongation test (temperature: 25 ° C.) using a tensile tester. (However, for an organic base material that does not extend up to 1.5 times, when it is extended up to 1.25 times), the extension rate S ₁ (%) of the difficult extension part 3 (of the extended length relative to the original length) The ratio is preferably 49% or less, more preferably 40% or less, still more preferably 25% or less, and particularly preferably 10% or less.

Moreover, the extensible organic base material of the present invention is stretched to 1.5 times (150% of the original length) in an extension test (temperature 25 ° C.) using a tensile tester. (However, for an organic base material that does not stretch up to 1.5 times, when stretched up to 1.25 times), the elongation rate S ₂ (%) of the extensible base material part ₂ (elongation to the original length) The ratio [S ₂ (%) / S ₁ (%)] between the ratio of the length) and the elongation rate S ₁ (%) of the difficult extension 3 is preferably greater than 1. In such an extensible organic base material, when the base material is extended in one direction, even if the extensible base material portion 2 is extended, the difficult extension portion 3 is not easily extended, and the shape is not easily changed. A desired design can be given to the difficult extension part 3, or a desired member can be fixed and held. The ratio [S ₂ (%) / S ₁ (%)] is more preferably 2 or more, and further preferably 5 or more (particularly 10 or more).

Furthermore, the stretchable organic base material is obtained when the stretchable organic base material is stretched to 1.5 times (150% of the original length) in a stretch test (temperature: 25 ° C.) using a tensile tester. (However, when the organic base material that does not stretch up to 1.5 times is stretched up to 1.25 times), the elongation rate S ₂ (%) of the extensible base material portion 2 and the elongation rate S of the difficult elongation portion 3 The difference of ₁ (%) [S ₂ (%) − S ₁ (%)] is preferably 20% or more, and more preferably 40% or more.

In the present invention, the extensibility of the extensible organic base material is preferably isotropic. For example, the elongation rate S ₂ (1) (%) of the extensible base material portion 2 in one direction and the elongation rate S ₂ (2) (2) of the extensible base material portion 2 in a direction orthogonal to the direction. %) [S ₂ (1) / S ₂ (2)] [where S ₂ (1) ≧ S ₂ (2)] is preferably 1 to 1.3, preferably 1 to 1.2. Is more preferable, and 1 to 1.1 is particularly preferable.

  The extensible organic substrate of the present invention may further have stretchability. When the extensible organic base material has stretchability, it can be suitably used in a field where stretchability is required such as a band member. By selecting a stretchable polymer as the polymer constituting the stretchable base material 2, stretchability can be imparted to the stretchable organic substrate 1. In such an extensible organic base material having stretchability, a hysteresis test at a 50% elongation using a tensile tester (test piece width 20 mm, chuck distance 50 mm, temperature 25 ° C., tensile speed 200 mm / min) The elongation recovery rate obtained is preferably 10% or more, more preferably 30% or more, still more preferably 50% or more (particularly preferably 70% or more).

Moreover, in the extensible organic base material of this invention, the extensible base material 2 is usually soft, and the difficult extension part 3 is hard. For example, in the extensible organic base material, a hardness test using a rubber hardness tester (10 pieces of an extensible organic base material of 30 mm × 30 mm test piece, hardness after 10 seconds of needle pushing, temperature 25 ° C. it is preferably greater than the ratio of the hardness H ₁ of the flame extension portion 3 and the hardness of H ₂ extensible base material ₂ (H ₁ / H 2) is 1 obtained by), and more preferably 1.01 or more, More preferably, it is 1.10 or more, Most preferably, it is 1.20 or more.

Moreover, a tensile elasticity modulus can also be used as a measure of the hardness of the extensible base material 2 and the difficultly stretchable portion 3. In the extensible organic base material, a solid viscoelasticity measuring device (sample size: length 25 mm × width 3 mm, distance between chucks: 5 mm, mode: time dispersion, temperature: 27 ° C., frequency: 1 Hz, initial strain: 0. 2%, measurement time: 120 sec, number of measurements: the ratio of the tensile modulus of the flame extension portion 3 as measured by 10 times) E _'1 (Pa) and a tensile modulus of extensibility base material ₂ E' 2 (Pa) (E ′ ₁ / E ′ ₂ ) is preferably larger than 1, more preferably 5 or more, further preferably 10 or more, and particularly preferably 100 or more.

Furthermore, the load in the nanoindentation measurement can also be used as a measure of the hardness of the extensible base material 2 and the difficultly elongated portion 3. The extensible in the organic substrate, the nano-indentation measurements the load P ₁ of the flame extension portion 3 in (indentation depth 4 [mu] m, indentation rate 1.5 [mu] m / sec, the temperature 25 ° C.) elongating the base material 2 of the load P ₂ The ratio (P ₁ / P ₂ ) is preferably greater than 1, more preferably 1.01 or more, still more preferably 1.10 or more, and particularly preferably 1.50 or more.

  In addition, the surface roughness Ra of the surface (at least one surface) of the extensible base material part 2 and the surface (at least one surface) of the formation site of the difficult extension part 3 is preferably 100 nm or less, more preferably 50 nm or less. Preferably, it is 30 nm or less. In particular, when precise members and parts are mounted on each surface, the smaller the surface roughness, the more accurately the members and parts can be installed, and the functions and performances of the members and parts are reliably exhibited. Can be made. Ra can be measured by an AFM (atomic force microscope).

[Extensible matrix (easily extensible polymer matrix)]
In the present invention, the extensible base material 2 can be composed of a polymer having extensibility (or further stretchability). An extensible base material (part) formed of a polymer is referred to as an easily extensible polymer base material (part). Examples of stretchable (or even stretchable) polymers include polyurethane polymers, polyurea polymers, polyurethane urea polymers, polyolefin polymers (particularly polydiene polymers), silicone polymers, polyester polymers, and polyethers. Polymer, polyamide polymer, polystyrene polymer, acrylic polymer having a low glass transition temperature (Tg) (Tg is, for example, less than 5 ° C, preferably 0 ° C or less, more preferably -5 ° C or less) Is mentioned. These polymers are usually flexible. These polymers can be used alone or in combination of two or more. The proportion of these polymers in the polymer constituting the easily stretchable polymer matrix is preferably 30% by weight or more, more preferably 50% by weight or more, still more preferably 70% by weight or more, and particularly preferably 90% by weight or more. It is.

  Among these, polyurethane polymer, polyurea polymer, polyurethane urea polymer, polyolefin polymer (particularly polydiene polymer), silicone polymer, polystyrene polymer (for example, styrene-isoprene-styrene block copolymer, styrene- Styrenic thermoplastic elastomers such as butadiene-styrene block copolymers are particularly preferred. Commercially available products (polymer alone, polymer aqueous dispersion, polymer organic solvent solution, etc.) can also be used as the polymer having extensibility (or further stretchability).

  In the present invention, the extensible base material (easily extensible polymer base material) 2 contains a weathering agent. It does not specifically limit as a weathering agent, A well-known weathering agent can be used. The weathering agent is preferably at least one selected from ultraviolet absorbers and antioxidants. A weathering agent can be used individually by 1 type or in combination of 2 or more types.

  Examples of the ultraviolet absorber as a weathering agent include at least one selected from benzotriazole compounds, hydroxyphenyltriazine compounds, salicylic acid ester compounds, benzophenone compounds, oxybenzophenone compounds, and cyanoacrylate compounds. . Only 1 type may be used for the ultraviolet absorber as a weatherproofing agent, and 2 or more types may be used together.

  Examples of the benzotriazole compounds include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole (TINUVIN PS, manufactured by BASF), benzenepropanoic acid and 3- (2H-benzotriazole-2). -Yl) -5- (1,1-dimethylethyl) -4-hydroxy (C7-9 side chain and linear alkyl) ester compound (TINUVIN 384-2, manufactured by BASF), octyl 3- [3-tert- Butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro- 2H-benzotriazol-2-yl) phenyl] propionate (TINUV N109, manufactured by BASF), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (TINUVIN900, manufactured by BASF), 2- (2H-benzo Triazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol (TINUVIN 928, manufactured by BASF), methyl-3- (3 -(2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product (TINUVIN 1130, manufactured by BASF), 2- (2H-benzotriazol-2- Yl) -p-cresol (TINUVIN P, manufactured by BASF), 2 (2H-benzotriazole-2) Yl) -4-6-bis (1-methyl-1-phenylethyl) phenol (TINUVIN234, manufactured by BASF), 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6 -(Tert-butyl) phenol (TINUVIN 326, manufactured by BASF), 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol (TINUVIN 328, manufactured by BASF), 2- (2H -Benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (TINUVIN 329, manufactured by BASF), 2-2'-methylenebis [6- (2H-benzotriazole-2- Yl) -4- (1,1,3,3-tetramethylbutyl) phenol] (TINUVIN 360, BASF Corporation) ), Methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol 300 (TINUVIN 213, manufactured by BASF), 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol (TINUVIN571, manufactured by BASF), 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimido-methyl) -5-methylphenyl] benzotriazole (Sumisorb 250, manufactured by Sumitomo Chemical Co., Ltd.), 2,2′-methylenebis [6- (benzotriazol-2-yl) -4-tert-octylphenol] (ADK STAB LA31, manufactured by ADEKA) Etc.

  Examples of the hydroxyphenyltriazine compound include 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl and [(C10-C16). Reaction product with (mainly C12-C13) alkyloxy) methyl] oxirane (TINUVIN 400, manufactured by BASF; 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2 -Yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol), 2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1, Reaction product of 3,5-triazine and (2-ethylhexyl) -glycidic acid ester (TINUVIN 405, manufactured by BASF), 2,4-bis “2-H Roxy-4-butoxyphenyl "-6- (2,4-dibutoxyphenyl) -1,3-5-triazine (TINUVIN460, manufactured by BASF), 2- (4,6-diphenyl-1,3,5-triazine -2-yl) -5-[(hexyl) oxy] -phenol (TINUVIN 1577, manufactured by BASF), 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [2- (2-Ethylhexanoyloxy) ethoxy] -phenol (ADK STAB LA46, manufactured by ADEKA), 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4- And phenylphenyl) -1,3,5-triazine (TINUVIN479, manufactured by BASF).

  Examples of benzophenone compounds and oxybenzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy Examples include -4,4'-dimethoxybenzophenone.

  Examples of salicylic acid ester compounds include phenyl-2-acryloyloxybenzoate, phenyl-2-acryloyloxy-3-methylbenzoate, phenyl-2-acryloyloxy-4-methylbenzoate, and phenyl-2. -Acryloyloxy-5-methylbenzoate, phenyl-2-acryloyloxy-3-methoxybenzoate, phenyl-2-hydroxybenzoate, phenyl-2-hydroxy-3-methylbenzoate, phenyl-2 -Hydroxy-4 methylbenzoate, phenyl-2-hydroxy-5-methylbenzoate, phenyl 2-hydroxy-3-methoxybenzoate, 2,4-di-tert-butylphenyl-3,5-di- tert-Butyl-4-hydroxybenzoate (TINUV N120, manufactured by BASF), and the like.

  Examples of the cyanoacrylate compound include alkyl-2-cyanoacrylate, cycloalkyl-2-cyanoacrylate, alkoxyalkyl-2-cyanoacrylate, alkenyl-2-cyanoacrylate, alkynyl-2-cyanoacrylate, and the like.

  Examples of the antioxidant as the weathering agent include at least one selected from a phenol stabilizer, a phosphorus stabilizer, a thioether stabilizer, and an amine stabilizer. Antioxidants as weathering agents are also called light stabilizers. Only 1 type may be used for the antioxidant (light stabilizer) as a weathering agent, and 2 or more types may be used together.

  Examples of the phenol-based stabilizer include 2,6-di-tert-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, and 2,6-di-tertiary. Butyl-4-ethylphenol, butylated hydroxyanisole, n-octadecyl-3- (4-hydroxy-3,5-di-tert-butylphenyl) propionate, distearyl- (4-hydroxy-3-methyl-5 -Tertiary butyl) benzyl malonate, tocopherol, 2,2'-methylenebis (4-methyl-6-tertiary butylphenol), 2,2'-methylenebis (4-ethyl-6-tertiary butylphenol), 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-butylidenebis (6-tertiarybutyl-m-cresol), 4, '-Thiobis (6-tertiarybutyl-m-cresol), styrenated phenol, N, N'-hexamethylenebis (3,5-di-tertiarybutyl-4-hydroxyhydrocinnamide, bis (3 , 5-Di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl ester) calcium, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3 , 5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [3- (3,5-di-tert-butyl-4-hydroxy) Phenyl) propionyloxymethyl] methane, 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -pcresol], 1,3,5-tris (4-tertiarybutyl-3-hydroxy- 2,6-dimethylbenzyl) isocyanuric acid, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, triethylene glycol-bis [3- (3-tertiary Tert-butyl-4-hydroxy-5-methylphenyl) propionate], 2,2′-oxamidobis [ethyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 6- (4- Hydroxy-3,5-di-tertiary butylanilino) -2,4-dioctylthio-1,3,5-triazine, bis [2-tertiary butyl-4-methyl-6- (2- Hydroxy-3-tertiarybutyl-5-methylbenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tertiarybutyl-4-hydroxy-5-methylphenyl) propionyloxy]- 1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis {2- [3- (3,5-di-tert-butyl-4) -Hydroxyphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5.5] undecane.

  Examples of phosphorus stabilizers include trisnonylphenyl phosphite, tris (2,4-di-tertiary butylphenyl) phosphite, tris [2-tertiary butyl-4- (3-tertiary butyl). -4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di Stearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl) -4-methylphenyl) pentaerythritol diphosphite, bis (2 , 4,6-Tri-tertiarybutylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-tertiary) Butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-tertiarybutylphenyl) butanetriphosphite, tetrakis (2,4-diter Tertiary butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (2-[(2,4,8,10-tetrakis-3rd Grade butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, etc. Is mentioned.

  Examples of the thioether-based stabilizer include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl, and distearyl; β-alkyl mercaptopropionate of polyols such as tetrakis [methylene (3-dodecylthio) propionate] methane Compound; and the like.

  Examples of amine stabilizers include dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol polymer (TINUVIN 622, manufactured by BASF), dimethyl succinate and 4-hydroxy. Polymer of 2,2,6,6-tetramethyl-1-piperidineethanol and N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- (N-methyl A one-to-one reaction product (TINUVIN119, with -2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine BASF), dibutylamine, 1,3-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyluro, 1,6-hexamethylenediamine) And N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate (TINUVIN2020, manufactured by BASF), poly [{6- (1,1,3,3-tetramethylbutyl) Amino-1,3,5-triazine-2-4-diyl} {2,2,6,6-tetramethyl-4-piperidyl} imino] hexamethylene {(2,2,6,6-tetramethyl-4 -Piperidyl) imino}) (TINUVIN 944, manufactured by BASF), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl A mixture of sebacate (TINUVIN765, manufactured by BASF), bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (TINUVIN770, manufactured by BASF), Bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester of candioic acid, reaction product of 1,1-dimethylethyl hydroperoxide and octane (TINUVIN123, manufactured by BASF) Bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate (TINUVIN 144, BASF) Product), cyclohexane and N-butyl peroxide 2,2,6,6-tetramethyl-4-piperidineamine-2,4,6-trichloro-1,3,5-triazine and 2-aminoethanol Reaction product (TINUVIN152, manufactured by BASF), bis (1,2,2,6,6 pentamethyl-4-piperidyl) Sebake And methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (TINUVIN 292, manufactured by BASF), 1,2,3,4-butanetetracarboxylic acid and 1,2,2, Mixed esterified product of 6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane (ADK STAB LA63P, manufactured by ADEKA). As the amine stabilizer, a hindered amine stabilizer is particularly preferable.

  The content (total amount) of the weathering agent in the extensible base material (easily extensible polymer base material) 2 is, for example, 0.001 to 10 with respect to the entire extensible base material (easily extensible polymer base material) 2. % By weight. The lower limit of the content (total amount) of the weathering agent is preferably 0.01% by weight, more preferably 0.1% by weight, still more preferably 0.3% by weight, and the upper limit is preferably 8% by weight. Preferably it is 6 weight%, More preferably, it is 5 weight%. In addition, when using a ultraviolet absorber as a weathering agent, the quantity is 0.001 to 10 weight% with respect to the whole extensible base material (easily extensible polymer base material) 2, for example, and a minimum is preferable Is 0.01% by weight, more preferably 0.1% by weight, still more preferably 0.3% by weight, and the upper limit is preferably 5% by weight, more preferably 3% by weight, still more preferably 2% by weight. is there. When an antioxidant is used as the weathering agent, the amount thereof is, for example, 0.001 to 10% by weight with respect to the entire extensible base material (easily extensible polymer base material) 2, and the lower limit is preferably 0. 0.01% by weight, more preferably 0.2% by weight, still more preferably 0.5% by weight, and the upper limit is preferably 5% by weight, more preferably 4% by weight, still more preferably 3% by weight.

  Only one of the ultraviolet absorber and the antioxidant (light stabilizer) can be used as the weathering agent, or both can be used in combination. Preferably, both are used together. Thereby, weather resistance can be remarkably improved.

  The stretchable polymer base material 2 is formed on a support, for example, by applying a composition in which a weathering agent is added to a liquid precursor of a polymer constituting the stretchable polymer base material to form a stretchable polymer base material. After forming the material layer for the material and arranging the material for forming the hardly-extensible polymer part at a predetermined portion of the material layer for forming the easily stretchable polymer matrix, the liquid precursor in the material layer for easily stretchable polymer matrix forming material It can be formed by converting the body to the desired polymer. Examples of the liquid precursor include a monomer that can be derived from the polymer (such as an energy ray-curable monomer), a partially polymerized product of the monomer, and a polymer that is precured or crosslinked that can be induced to the polymer by curing or crosslinking. The conversion of the liquid precursor into a target polymer can be performed by, for example, polymerization (energy ray or heat polymerization), curing, cross-linking reaction, or the like.

  Further, the easily stretchable polymer base material portion 2 is formed, for example, on a support by applying a solution or dispersion containing a polymer constituting the easily stretchable polymer base material and a weathering agent to form an easily stretchable polymer base material. After forming the material layer for forming and forming the material for forming the hardly-extensible polymer portion at a predetermined portion of the material layer for forming the easily stretchable polymer base material, the solvent in the material layer for forming the easily stretchable polymer base material is used. It can also be formed by drying. The solvent used in the solution containing the polymer may be any solvent that can dissolve the polymer. Examples thereof include esters such as ethyl acetate; hydrocarbons such as aromatic hydrocarbons such as toluene; ketones such as acetone; methylene chloride and the like. Halocarbons; lactones; amides; lactams; water; and mixed solvents thereof. Examples of the dispersion containing the polymer include an aqueous dispersion (such as a reaction liquid after emulsion polymerization).

  Furthermore, the easily extensible polymer base material part 2 forms, on a support, for example, an easily extensible polymer base material forming material layer by a mixture of a single polymer constituting the easily extensible polymer base material and a weathering agent, It can also be formed by performing a melting / cooling process (hot melt process) after disposing a forming material for the hardly extensible polymer part at a predetermined portion of the easily extensible polymer base material forming material layer. In this case, the easily stretchable polymer base material forming material layer is obtained by subjecting the mixture of the polymer alone and the weathering agent to a general film molding method (extrusion molding, injection molding, compression molding, hot melt treatment, etc.). Can be formed. In this case, the easily stretchable polymer base material forming material layer and the easily stretchable polymer base material are often composed of substantially the same material composition. The melting / cooling treatment means cooling after melting.

In the present invention, the easily stretchable polymer base material part 2 includes, for example, a polyurethane chain, a polyurea chain, a polyurethane urea chain, a polyolefin chain (particularly, a polydiene chain), a silicone chain, a polyester chain, a polyether chain, a polyamide chain, and a polystyrene series. A mixture of a curable polymer P and a weathering agent having at least one polymer chain selected from the group consisting of a polymer chain and a polyacryl chain, and having an energy ray-curable group A ₁ in the main chain or side chain, or It can be formed by irradiating a mixture of the curable polymer P, a curable monomer M having an energy ray curable group A ₂ and a weathering agent by irradiating with energy rays. The curable polymer P and the mixture of the curable polymer P and the curable monomer M having the energy ray curable group A ₂ are precursors of the polymer.

  Examples of the energy rays include ionizing radiation such as α rays, β rays, γ rays, neutron rays, and electron rays, ultraviolet rays, and visible rays. Among these, ultraviolet rays and electron beams are preferable, and ultraviolet rays are particularly preferable.

Examples of the energy ray-curable groups A ₁ and A ₂ include a group containing a carbon-carbon unsaturated bond (a group containing a radical polymerizable group) such as a (meth) acryloyl group or a vinyl group, an epoxy group, And cationically polymerizable groups such as oxetanyl group. When the energy ray-curable groups A ₁ in the curable polymer P having an energy ray-curable groups A ₁ is a group containing a radically polymerizable group in the main chain or side chain, having an energy ray-curable groups A ₂ The energy ray curable group A _{2 in the} curable monomer M is also preferably a group containing a radical polymerizable group, and the energy ray curable property in the curable polymer P having the energy ray curable group A ₁ in the main chain or side chain. When the group A ₁ is a cationic polymerizable group, the energy beam curable group A ₂ in the curable monomer M having the energy beam curable group A ₂ is also preferably a cationic polymerizable group.

The curable polymer P includes a compound having an energy ray curable group A ₁ and a reactive functional group R ₁ , and a reactive functional group R ₂ having reactivity to the reactive functional group R ₁ in the molecule. And at least one selected from the group consisting of a polyurethane chain, a polyurea chain, a polyurethane urea chain, a polyolefin chain (particularly a polydiene chain), a silicone chain, a polyester chain, a polyether chain, a polyamide chain, and a polyacryl chain. It can be obtained by reacting with a polymer having a polymer chain.

Examples of the combination (regardless of order) of the reactive functional group R ₁ and the reactive functional group R ₂ include a combination of a hydroxyl group and an isocyanate group, a combination of a hydroxyl group and an epoxy group, a carboxyl group, or an acid anhydride. A combination of a compound group and an isocyanate group, a combination of a carboxyl group or an acid anhydride group and an epoxy group, a combination of an amino group and an isocyanate group, a combination of an amino group and an epoxy group, a Si-H group and a carbon-carbon group. A combination with a group having a heavy bond is exemplified.

A polymer having a reactive functional group R ₂ and a polyurethane chain can be prepared by combining a polyisocyanate compound, a long-chain polyol compound, and a chain extender or other isocyanate-reactive compound used as necessary. It can obtain by making it react.

  Examples of the polyisocyanate compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate, and norbornane diisocyanate; naphthalene diisocyanate, Aromatic diisocyanates, such as phenylene diisocyanate, tolylene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, diphenyl ether diisocyanate, diphenylpropane diisocyanate; xylylene diisocyanate, tetramethylene xylylene diisocyanate, etc. ; And dimer acid diisocyanate.

  Examples of the long-chain polyol compound include polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, and polyacryl polyol. The number average molecular weight of the long-chain polyol is usually 500 or more, preferably 500 to 10000, more preferably 550 to 4000. Long chain polyols can be used alone or in combination of two or more.

  Examples of the polyether polyol include polyalkylene ether glycols such as polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol (PTMG), and a plurality of alkylene oxides as monomer components such as an ethylene oxide-propylene oxide copolymer. (Alkylene oxide-other alkylene oxide) copolymer containing etc. are mentioned.

  Examples of the polyester polyol include a condensation polymer of a polyhydric alcohol and a polyvalent carboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a reaction by three kinds of components: a polyhydric alcohol, a polyvalent carboxylic acid, and a cyclic ester. Things can be used. In the condensation polymerization product of polyhydric alcohol and polycarboxylic acid, examples of polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1 , 3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediol (Such as 1,4-cyclohexanediol), cyclohexanedimethanols (such as 1,4-cyclohexanedimethanol), bisphenols (such as bisphenol A), sugar alcohols (such as xylitol and sorbitol), etc. Kill. On the other hand, examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids such as malonic acid, maleic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; 1,4-cyclohexanedicarboxylic acid, etc. And aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid and trimellitic acid. In the ring-opening polymer of cyclic ester, examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone. In the reaction product of the three types of components, those exemplified above can be used as the polyhydric alcohol, polycarboxylic acid, and cyclic ester.

  Examples of the polycarbonate polyol include a reaction product of a polyhydric alcohol and phosgene, chloroformate, dialkyl carbonate or diaryl carbonate; a ring-opening polymer of a cyclic carbonate (such as alkylene carbonate). Specifically, in the reaction product of polyhydric alcohol and phosgene, the polyhydric alcohol includes the polyhydric alcohols exemplified above (for example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol). , Neopentyl glycol, 1,6-hexanediol, etc.) can be used. In the ring-opening polymer of cyclic carbonate, examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like. In addition, the polycarbonate polyol should just be a compound which has a carbonate bond in a molecule | numerator, and the terminal is a hydroxyl group, and may have an ester bond with a carbonate bond. Representative examples of polycarbonate polyols include polyhexamethylene carbonate diol, diol obtained by ring-opening addition polymerization of lactone to polyhexamethylene carbonate diol, and cocondensate of polyhexamethylene carbonate diol with polyester diol or polyether diol. Etc.

  The polyolefin polyol is a polyol having an olefin as a component of the skeleton (or main chain) of the polymer or copolymer and having at least two hydroxyl groups in the molecule (particularly at the terminal). The olefin may be an olefin having a carbon-carbon double bond at the terminal (for example, an α-olefin such as ethylene or propylene), or an olefin having a carbon-carbon double bond at a position other than the terminal. (For example, isobutene and the like) and diene (for example, butadiene, isoprene and the like) may be used. Typical examples of polyolefin polyols include butadiene homopolymers, isoprene homopolymers, butadiene-styrene copolymers, butadiene-isoprene copolymers, butadiene-isoprene copolymers such as butadiene-modified polymers modified with hydroxyl groups at the ends. .

The polyacrylic polyol is a polyol having (meth) acrylate as a component of the polymer (or copolymer) skeleton (or main chain) and having at least two hydroxyl groups in the molecule (particularly at the terminal). As the (meth) acrylate, (meth) acrylic acid alkyl ester [for example, (meth) acrylic acid C _1-20 alkyl ester, etc.] is preferably used.

  As the chain extender, a chain extender usually used in the production of thermoplastic polyurethane can be used, and the kind thereof is not particularly limited, but a low molecular weight polyol, polyamine or the like can be used. The molecular weight of the chain extender is usually less than 500, preferably 300 or less. A chain extender can be used individually or in combination of 2 or more types.

  Representative examples of chain extenders include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, Polyols (especially diols) such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; hexamethylenediamine, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-methylenebis- Examples include polyamines such as 2-chloroaniline (particularly diamines).

  Examples of the polymer having a polyurethane chain include a polyisocyanate compound, a long-chain polyol compound, and, if necessary, a chain extender and another isocyanate-reactive compound, the number of moles of isocyanate groups of the polyisocyanate, and a long-chain polyol. And the ratio (NCO / isocyanate reactive group) to the number of moles of isocyanate reactive groups (hydroxyl group, amino group, etc.) of the chain extender and the like is 0.8 to 2.0, particularly 0.95 to 1.5. What was obtained by making it react in the range which becomes is preferable. In order to accelerate the reaction, a catalyst such as a tertiary amine, an organometallic compound, or a tin compound may be used in the above reaction as necessary.

If the end of a polymer having a polyurethane chain is an isocyanate group can utilize the isocyanate group as a reactive functional group R _2. In this case, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, etc. can be used as the compound having the energy ray curable group A ₁ and the reactive functional group R ₁ .

Further, when the end of the polymer having a polyurethane chain is a hydroxyl group, it can be used the hydroxyl groups as reactive functional groups R _2. In this case, (meth) acryloyloxyethyl isocyanate or the like can be used as the compound having the energy ray curable group A ₁ and the reactive functional group R ₁ .

Polymer having reactive functional group R ₂ and having polyurea chain, polymer having reactive functional group R ₂ and having polyurethane urea chain, polyolefin having reactive functional group R ₂ and polyolefin chain (particularly polydiene chain) ), A reactive functional group R ₂ and a silicone chain, a reactive functional group R ₂ and a polyester chain, a reactive functional group R ₂ and a polyether chain , A polymer having a reactive functional group R ₂ and a polyamide chain, and a polymer having a reactive functional group R ₂ and a polyacryl chain can also be obtained by a known or conventional method.

Then, the polymer and having a specific polymer chains having these reactive functional groups R _2, depending on the type of reactive functional group R ₂ having the said polymer, said energy ray-curable groups A ₁ and reactive By reacting the compound having the functional group R ₁ , the curable polymer P having the energy ray curable group A ₁ in the main chain or the side chain can be produced.

In the present invention, as the curable monomer M having the energy ray curable group A ₂ , a compound having a group (radical polymerizable group) containing a carbon-carbon unsaturated bond such as a (meth) acryloyl group or a vinyl group; Examples thereof include compounds having a cationically polymerizable group such as an epoxy group and an oxetanyl group. Among these, a compound containing a radical polymerizable group is preferable. Incidentally, curable monomers M having an energy ray-curable groups A ₂ may be used in combination of at least one kind alone, or two or.

In the curable monomer M having energy ray-curable group A _2, a compound energy ray-curable groups and A ₂ is a radical polymerizable group, e.g., methyl (meth) acrylate, (meth) acrylate, ( Meth) propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) Pentyl acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, (meth ) Nonyl acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylate Isodecyl sulfate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid C _1-20 alkyl esters such as heptadecyl acid, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate (Meth) acrylic acid ester having an alicyclic group such as isobornyl (meth) acrylate; aromatic hydrocarbon group such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate (Meth) acrylic acid ester having T) Alkoxyalkyl (meth) acrylates such as methoxyethyl acrylate and ethoxyethyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid 3 -Hydroxypropyl, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, vinyl alcohol, allyl alcohol and other hydroxyl group (hydroxyl group) -containing monomers; (meth) acrylic acid, itaconic acid, crotonic acid , Maleic acid, fumaric acid, isocrotonic acid, maleic anhydride, itaconic anhydride, 2-carboxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, etc. No carboxyl group or acid Monomer group-containing monomers; sulfonic acid group-containing monomers such as sodium vinyl sulfonate, allyl sulfonic acid, styrene sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate; phosphorus such as 2-hydroxyethyl acryloyl phosphate Acid group-containing monomers; Epoxy group-containing monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N Amido group-containing monomers such as methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide; N-vinyl-2-pyrrolidone, N-vinyl-2-piperide N-vinyl-2-caprolactam, N-vinyl piperazine, N-vinyl pyrrole, N-vinyl imidazole, nitrogen-containing heterocycle-containing monomers such as (meth) acryloylmorpholine; and (meth) acrylic acid tetrahydrofurfuryl Oxygen heterocycle-containing monomers; amino group-containing monomers such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; cyano groups such as acrylonitrile and methacrylonitrile Monomer; Imido group-containing monomer such as cyclohexylmaleimide and isopropylmaleimide; Isocyanate group-containing monomer such as 2-methacryloyloxyethyl isocyanate; Styrenic monomer such as styrene, α-methylstyrene, vinyltoluene; Olefin monomers such as tylene, propylene, isoprene, butadiene, isobutylene; vinyl ester monomers such as vinyl acetate and vinyl propionate; vinyl ether monomers such as vinyl alkyl ether; vinyl chloride; vinylidene chloride; (Meth) acrylic acid ester; (meth) acrylic acid ester having a silicon atom-containing group.

In the curable monomer M having energy ray-curable group A _2, a compound energy ray-curable groups and A ₂ is a radical polymerizable group, In addition to the above, 1,6-hexanediol di (meth) acrylate, 1 , 4-butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, trimethyl Uses polyfunctional monomers such as roll propane EO-added tri (meth) acrylate, glycerin PO-added tri (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate You can also “EO” represents ethylene oxide, and “PO” represents propylene oxide.

In the curable monomer M having energy ray-curable group A _2, a compound energy ray-curable groups and A ₂ is a cationic polymerizable group, an epoxy group, a known compound having a cationically polymerizable group such as oxetanyl group Can be used.

Among the curable monomers M having the energy ray curable group A ₂ , curable monomers having a radical polymerizable group are preferable. In particular, it is preferable to use at least (meth) acrylic acid C _1-20 alkyl ester as the curable monomer M. Further, in order to improve the adhesion strength at the interface between the easily extensible polymer base material 2 and the hardly extensible polymer portion 3, the same kind of monomer as the polymer constituting the hardly extensible polymer portion as the curable monomer M (particularly, It is also preferred to use the same monomer).

When (meth) acrylic acid C _1-20 alkyl ester is used as curable monomer M, the proportion of (meth) acrylic acid C _1-20 alkyl ester in the entire curable monomer is, for example, 40% by weight or more (40 to 40% or more). 100% by weight), preferably 50% by weight or more (50-100% by weight), more preferably 60% by weight or more (60-100% by weight). Further, as the curable monomer M, together with a (meth) acrylic acid C _1-20 alkyl ester, a carboxyl group such as (meth) acrylic acid or an anhydride group-containing monomer, or a hydroxyl group such as 2-hydroxyethyl (meth) acrylate Containing monomers may be used. In this case, the use amount of the carboxyl group- or acid anhydride group-containing monomer and the hydroxyl group-containing monomer is, for example, in the range of 0 to 50% by weight (about 0.1 to 50% by weight), respectively, with respect to the entire curable monomer. It may be selected from about 1 to 45% by weight.

  As described above, the easily stretchable polymer base material 2 is cured by irradiating the mixture of the curable polymer P and the weathering agent, or the mixture of the curable polymer P, the curable monomer M, and the weathering agent with energy rays. Can be formed. At this time, a photopolymerization initiator is usually used.

When the energy ray curable groups A ₁ and A ₂ are radical polymerizable groups, examples of the photopolymerization initiator include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, and α-ketol photopolymerization initiators. Agent, aromatic sulfonyl chloride photopolymerization initiator, photoactive oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone photopolymerization initiator, ketal photopolymerization initiator, thioxanthone A system photopolymerization initiator or the like is used.

  Examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one, Anisole methyl ether etc. are mentioned. Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, and 4- (t-butyl). ) Dichloroacetophenone and the like. Examples of the α-ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one. It is done. Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride. Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime. Examples of the benzoin photopolymerization initiator include benzoin. Examples of the benzyl photopolymerization initiator include benzyl. Examples of the benzophenone photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinyl benzophenone, α-hydroxycyclohexyl phenyl ketone, and the like. Examples of the ketal photopolymerization initiator include benzyl dimethyl ketal. Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.

When the energy ray curable groups A ₁ and A ₂ are cationic polymerizable groups, a known or conventional cationic curing catalyst can be used as a photopolymerization initiator.

  Although it does not specifically limit as the usage-amount of a photoinitiator, It is 0.01-3 weight part with respect to 100 weight part of sclerosing | hardenable compound whole quantity, The upper limit becomes like this. Preferably it is 1 weight part, More preferably The lower limit is preferably 0.02 parts by weight, more preferably 0.05 parts by weight.

  In the present invention, in the polymer having stretchability (or further stretchability) constituting the easily stretchable polymer matrix 2, polyurethane chain, polyurea chain, polyurethaneurea chain, polyolefin chain (particularly polydiene chain), silicone chain, polyester In the case of having at least one polymer chain selected from the group consisting of a chain, a polyether chain and a polyamide chain, the proportion of the at least one polymer chain portion in the whole polymer is 20% by weight or more (for example, 20 to 100% by weight) is preferable, more preferably 25% by weight or more (for example, 25 to 90% by weight), and still more preferably about 30% by weight or more (for example, 30 to 75% by weight). If this ratio is too small, the extensibility tends to decrease. In addition, the polymer having stretchability (or further stretchability) constituting the stretchable polymer base material 2 is an acrylic polymer having a low glass transition temperature (Tg) (Tg is, for example, less than 5 ° C., preferably 0 ° C. or less. In the case of an acrylic polymer having a temperature of −5 ° C. or lower), the ratio of the polyacryl chain in the whole polymer may be 100% by weight.

  In the easily extensible polymer base material part 2, for example, a crosslinking agent (for example, an isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a urea crosslinking agent, Metal alkoxide crosslinking agent, metal chelate crosslinking agent, metal salt crosslinking agent, carbodiimide crosslinking agent, oxazoline crosslinking agent, aziridine crosslinking agent, amine crosslinking agent, etc.), crosslinking accelerator, silane coupling agent, adhesive Additive resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), fillers, colorants (pigments, dyes, etc.), plasticizers, softeners, surfactants, antistatic agents and other additives It may be included within a range not impairing the characteristics of the invention.

[Hard stretchable part (hard stretchable polymer part)]
In the present invention, the material constituting the hardly stretchable part 3 is usually a polymer material containing at least a polymer. Such a hardly stretchable portion is referred to as a hardly stretchable polymer portion. This polymer material may contain a filler (inorganic filler, organic filler). The polymer in the polymer material may be a single type or a mixture of two or more types.

  As the hardly extensible polymer part 3, for example, (i) a monomer having a Tg of homopolymer of 5 ° C. or higher (more preferably 15 ° C. or higher, more preferably 50 ° C. or higher) [particularly, (meth) acrylic monomer] A polymer containing 50% by weight or more (more preferably 60% by weight or more, and still more preferably 80% by weight or more) based on the total structural unit of the polymer [for example, Tg is 5 ° C. or more, preferably Polymer material containing polymer of 15 ° C. or higher (particularly acrylic polymer)], (ii) Configuration derived from polyfunctional monomer having two or more curable groups (radical polymerizable group, cationic polymerizable group) in the molecule A polymer containing 50% by weight or more (more preferably 60% by weight or more, and further preferably 80% by weight or more) of the unit with respect to all structural units of the polymer Therefore, the structural unit derived from a polyfunctional monomer having 2 or more radical polymerizable groups in the molecule (particularly an acrylic polyfunctional monomer) is 50% by weight or more (more preferably 60% by weight) based on the total structural unit of the polymer. (Iii) a filler-containing polymer material, (iv) a tensile modulus of elasticity of 0.1 MPa or more (more preferably 0.5 MPa or more, It is preferably 1 MPa or more, particularly preferably 5 MPa or more.

  In the case of (i), the polymer material constituting the hardly extensible polymer part of the polymer containing 50% by weight or more of the structural unit derived from the monomer whose Tg of the homopolymer is 5 ° C. or higher with respect to all the structural units of the polymer The ratio to the whole is, for example, 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, and may be 50% by weight or more (for example, 90% by weight or more). In the case of (ii), it constitutes a hardly extensible polymer part of a polymer containing 50% by weight or more of structural units derived from a polyfunctional monomer having two or more curable groups in the molecule based on the total structural units of the polymer. The proportion of the entire polymer material is, for example, 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, and may be 50% by weight or more (for example, 90% by weight or more).

In (i) above, examples of the monomer having a Tg of homopolymer of 5 ° C. or higher include alicyclic rings such as isobornyl acrylate (homopolymer Tg: 97 ° C.) and cyclohexyl acrylate (homopolymer Tg: 15 ° C.). (Meth) acrylic acid ester having a formula group; (meth) acrylic acid tertiary alkyl ester such as t-butyl acrylate (homopolymer Tg: 41 ° C.); methyl methacrylate (homopolymer Tg: 105 ° C.); Methacrylic acid C _1-4 alkyl esters such as ethyl methacrylate (Tg of homopolymer: 65 ° C.), butyl methacrylate (Tg of homopolymer: 20 ° C.), isobutyl methacrylate (Tg of homopolymer: 67 ° C.); styrene Styrenic monomers such as (Tg of homopolymer: 100 ° C.); acrylonitrile (Homopolymer Tg: 100 ° C.).

  In the above (ii), as the polyfunctional monomer, for example, 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly ) Propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, trimethylolpropane EO-added tri (meth) acrylate, glycerin PO-added tri (meth) acrylate Rate and the like. Among the polyfunctional monomers, those having 3 or more functional groups (for example, 3 to 6 functional groups) are most preferable.

  In (iii) above, examples of the filler include inorganic oxides such as silica, alumina, titanium oxide, zirconium oxide, iron oxide, copper oxide, zinc oxide, and tin oxide; nitrides such as boron nitride and aluminum nitride; carbonic acid Carbonates such as calcium and magnesium carbonate; clay minerals such as mica, smectite, kaolinite, montmorillonite, vermiculite; metals such as gold, silver, copper, iron, nickel, zinc, aluminum, tin (including metal alloys); glass And inorganic fillers; organic fillers and the like. The filler may have a core / shell structure that is surface-treated and coated with an appropriate component. Furthermore, the filler may have a hollow structure such as a glass balloon, a ceramic balloon, a fly ash balloon, or hollow silica. A filler can be used individually by 1 type or in combination of 2 or more types. By using the filler, not only the hardly extensible polymer portion 3 can be imparted with difficulty extensibility and hardness, but various functions such as conductivity and thermal conductivity can be imparted depending on the type of filler.

  The shape of the filler is not particularly limited, and may be any of a bulk shape, a spherical shape, a needle shape, a plate shape, and the like. Moreover, the average particle diameter of the filler (in the case of needles, the average diameter of the major axis) is, for example, 0.001 to 100 μm. The upper limit of the average particle diameter of the filler (in the case of needles, the average diameter of the major axis) is preferably 50 μm, more preferably 20 μm, and the lower limit is preferably 0.005 μm, more preferably 0.008 μm.

  The “polymer” in the filler-containing polymer material is not particularly limited, and the polymer exemplified as the polymer constituting the easily extensible polymer matrix and the (i) homopolymer exemplified as the polymer constituting the hardly extensible polymer portion 3. (Ii) Curability exemplified as a polymer comprising 50% by weight or more of a structural unit derived from a monomer having a polymer Tg of 5 ° C. or higher, and a polymer constituting the hardly extensible polymer part 3 (Iv) Tensile described later as a polymer comprising 50% by weight or more of a structural unit derived from a polyfunctional monomer having two or more groups in the molecule, based on the total structural unit of the polymer, and a polymer constituting the hardly extensible polymer part 3 Any of polymers having an elastic modulus of 0.1 MPa or more may be used. The polymer may be an energy ray curable polymer.

  In (iv), the polymer having a tensile modulus of elasticity of 0.1 MPa or more is not particularly limited as long as the polymer has a tensile modulus of elasticity of 0.1 MPa or more (a mixture of one or two or more polymers). , Polyurethane polymer, polyurea polymer, polyurethane urea polymer, polyolefin polymer, silicone polymer, polyester polymer, polyether polymer, polyamide polymer, polystyrene polymer, acrylic polymer, etc. it can. When two or more kinds of polymers are contained, the tensile modulus of the polymer mixture may be 0.1 MPa or more.

  As a typical example of a polymer having a tensile modulus of elasticity of 0.1 MPa or more, for example, a polyurethane-based polymer having a Tg of 5 ° C. or more (more preferably 20 ° C. or more); a styrene-butadiene-styrene block copolymer (SBS) Polystyrene polymers such as hydrogenated product (SEBS) and hydrogenated product (SEPS) of styrene-isoprene-styrene block copolymer (SIS); and acrylic polymers such as polymethyl methacrylate. As a polymer material having a tensile modulus of elasticity of 0.1 MPa or more, it is preferable to contain these polymers, for example, 50% by weight or more, particularly 80% by weight or more.

  The hardly extensible polymer part 3 includes a polymer part formed by converting a precursor of a polymer material constituting the hardly extensible polymer part 3 into the polymer material, and a solvent in the solution or dispersion containing the polymer material. Any of a polymer part formed by drying and removing, a polymer part formed by melting and cooling the polymer material, and the like may be used.

The hardly extensible polymer part 3 is composed of a polymer material containing a polymer containing (i) 50% by weight or more of a structural unit derived from a monomer having a Tg of a homopolymer of 5 ° C. or higher based on the total structural unit of the polymer. In this case, for example, after arranging a monomer component containing 50% by weight or more of the monomer having a Tg of 5 ° C. or more of the homopolymer at a predetermined portion of the easily extensible polymer base material forming material layer, energy rays Can be formed by curing (polymerization). In this case, as a monomer other than the monomer having a homopolymer Tg of 5 ° C. or more, for example, a monomer exemplified as the curable monomer M having the energy ray curable group A ₂ can be appropriately selected and used.

A polymer material containing a polymer containing 50% by weight or more of a structural unit derived from a polyfunctional monomer having (ii) two or more curable groups in the molecule, based on the total structural unit of the polymer, the hard-extensible polymer part 3 For example, after arranging a monomer component containing the polyfunctional monomer in an amount of 50% by weight or more of the entire monomer at a predetermined portion of the easily stretchable polymer base material forming material layer, irradiation with energy rays and curing ( Polymerization). In this case, as a monomer other than the polyfunctional monomer, a monofunctional monomer can be appropriately selected from the monomers exemplified as the curable monomer M having the energy ray curable group A ₂ .

  When forming the hardly extensible polymer part 3, a photopolymerization initiator is usually used to cure the curable group. It does not specifically limit as a photoinitiator, The photoinitiator similar to the case where the said easily extensible polymer base material 2 is formed can be used. Although it does not specifically limit as the usage-amount of a photoinitiator, It is 0.01-3 weight part with respect to 100 weight part of sclerosing | hardenable compound whole quantity, The upper limit becomes like this. Preferably it is 1 weight part, More preferably The lower limit is preferably 0.02 parts by weight, more preferably 0.05 parts by weight.

  In the case where the hardly extensible polymer portion 3 is composed of the above-mentioned (iii) filler-containing polymer, a dispersion containing a filler (an aqueous dispersion, an organic solvent) at a predetermined portion of the easily extensible polymer base material forming material layer After the dispersion or the like is disposed, the hardly extensible polymer portion 3 can be formed by drying and removing the solvent in the dispersion. In this case, the hardly extensible polymer portion 3 is composed of the filler and the same polymer as the polymer constituting the easily extensible polymer base material 2. In the case where the material layer for forming an easily stretchable polymer base material is formed from an organic solvent solution of a polymer constituting the layer, it is preferable to use an organic solvent dispersion of a filler. When the forming material layer is formed with an aqueous dispersion of the polymer constituting the layer, it is preferable to use an aqueous dispersion of filler. In addition, a filler and a monomer (such as an energy ray-curable monomer) that can be derived into a polymer that should form a hardly extensible polymer portion or a partial polymer thereof are necessary at a predetermined portion of the easily extensible polymer base material forming material layer. The hard-to-extend polymer part 3 can be formed by polymerizing the monomer or a partial polymer thereof after arranging a mixed solution containing a solvent according to the above. Furthermore, after arranging a mixed liquid containing a filler, a pre-crosslinking polymer that can be induced by crosslinking to a polymer that should constitute a hardly extensible polymer portion, and a crosslinking agent at a predetermined portion of the material layer for forming an easily stretchable polymer base material A hardly extensible polymer part can be formed by crosslinking the polymer before crosslinking. Furthermore, after placing the filler alone (powder) at a predetermined part of the easily stretchable polymer matrix forming material layer, the easily stretchable polymer matrix forming material layer is converted into an easily stretchable polymer matrix. Thus, a hardly extensible polymer portion can be formed at the same time. In this case, the hardly extensible polymer portion is composed of the filler and the same polymer as the polymer constituting the easily extensible polymer base material. The usage-amount of a filler can be suitably adjusted with the magnitude | size of the difficulty extensible polymer part to form, the intensity | strength of the difficult extensible polymer part desired, etc. For example, the filler content in the hardly extensible polymer part 3 is, for example, about 0.1 to 99% by weight, and the upper limit thereof is preferably 95% by weight, more preferably 90% by weight, particularly preferably 80% by weight. The lower limit is preferably 1% by weight, more preferably 5% by weight, and particularly preferably 10% by weight.

  When the hardly extensible polymer part 3 is composed of (iv) a polymer material having a tensile modulus of elasticity of 0.1 MPa or more, a monomer (such as an energy ray-curable monomer) that can be derived from the polymer or a partial polymer thereof is used. The hardly extensible polymer part 3 can be formed by polymerizing, or curing or crosslinking a polymer that can be induced by curing or crosslinking to the polymer.

  The hard-extensible polymer part (hard-extendable part) 3 may contain a weathering agent in the same manner as the easy-extensible polymer base part (extensible base part) 2. By adding a weathering agent to the hardly extensible polymer portion (hardly extensible portion), deterioration of the extensible organic base material outdoors can be suppressed more remarkably. The same weathering agent as described above can be used.

  The content (total amount) of the weathering agent in the hardly extensible polymer portion (hardly stretchable portion) 3 is, for example, 0.001 to 10% by weight with respect to the whole difficult stretchable polymer portion (hardly stretchable portion) 3. The lower limit of the content (total amount) of the weathering agent is preferably 0.01% by weight, more preferably 0.1% by weight, still more preferably 0.3% by weight, and the upper limit is preferably 8% by weight. Preferably it is 6 weight%, More preferably, it is 5 weight%. In addition, when using a ultraviolet absorber as a weathering agent, the amount is 0.001 to 10 weight% with respect to the whole difficulty extensible polymer part (hardly stretchable part) 3, for example, and a minimum is preferably 0. 0.01% by weight, more preferably 0.1% by weight, still more preferably 0.3% by weight, and the upper limit is preferably 5% by weight, more preferably 3% by weight, still more preferably 2% by weight. When using an antioxidant as a weathering agent, the amount thereof is, for example, 0.001 to 10% by weight with respect to the whole of the hardly stretchable polymer part (hardly stretched part) 3, and the lower limit is preferably 0.01. The upper limit is preferably 5% by weight, more preferably 4% by weight, still more preferably 3% by weight.

  Only one of the ultraviolet absorber and the antioxidant (light stabilizer) can be used as a weathering agent in the hardly extensible polymer part (hardly extending part) 3, or both can be used in combination. it can. Preferably, both are used together. Thereby, weather resistance can be remarkably improved.

  For the hardly extensible polymer part 3, for example, a crosslinking agent (for example, an isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a urea crosslinking agent, a metal alkoxide is used as necessary. Crosslinking agent, metal chelate crosslinking agent, metal salt crosslinking agent, carbodiimide crosslinking agent, oxazoline crosslinking agent, aziridine crosslinking agent, amine crosslinking agent, etc.), crosslinking accelerator, silane coupling agent, tackifying resin (Rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), fillers, colorants (pigments, dyes, etc.), plasticizers, softeners, surfactants, antistatic agents, and other additives of the present invention It may be included within a range that does not impair the characteristics.

  Of the materials constituting the hardly extensible polymer part, the polymer is the same as the polymer constituting the easily extensible polymer matrix from the viewpoint of the integrity and adhesion of the easily extensible polymer matrix and the hardly extensible polymer member. Or a polymer having a polymer chain of the same type as the polymer chain (main chain or side chain) of the polymer constituting the easily stretchable polymer matrix in the main chain or side chain.

  More specifically, as a preferred combination of the polymer constituting the easily extensible polymer matrix and the polymer constituting the hardly extensible polymer portion, a combination of polyurethane polymers, a combination of polyurea polymers, a polyurethane urea polymer Combinations of polyolefin polymers, combinations of silicone polymers, combinations of polyester polymers, combinations of polyether polymers, combinations of polyamide polymers, combinations of polystyrene polymers, acrylic polymers The combination of these is mentioned. A combination of a polystyrene polymer and an acrylic polymer is also preferable. Furthermore, as the preferred combination, a combination of polymers having a polyurethane chain, a combination of polymers having a polyurea chain, a combination of polymers having a polyurethane urea chain, a combination of polymers having a polyolefin chain, and a polymer having a silicone chain Combination of polymers having a polyester chain, combination of polymers having a polyether chain, combination of polymers having a polyamide chain, combination of polymers having a polystyrene-based polymer chain, between polymers having a polyacryl chain Combinations are mentioned.

  Among these, as a preferable combination of the polymer constituting the easily extensible polymer matrix and the polymer constituting the hardly extensible polymer portion, a combination of polyurethane polymers, a combination of polymers having a polyurethane chain, and a combination of polystyrene polymers A combination, a combination of polymers having a polystyrene polymer chain, a combination of acrylic polymers, a combination of polymers having a polyacryl chain, and a combination of a polystyrene polymer and an acrylic polymer are particularly preferable.

[Manufacture of extensible organic substrate]
The extensible organic base material of this invention can be manufactured by passing through the following process A, process B, and process C, for example.
Step A: On the support, a liquid mixture of the polymer (a) liquid precursor and the weathering agent constituting the easily extensible polymer matrix, a solution or dispersion containing the polymer (a) and the weathering agent, or the above Step of forming an easily extensible polymer base material forming material layer with a mixture of the polymer (a) alone and a weathering agent Step B: In a predetermined part of the easily extensible polymer base material forming material layer, a hardly extensible polymer portion Arranging the forming material;
Step C: At least one selected from a reaction, a solvent drying removal process, and a melting / cooling process on the easily stretchable polymer base material forming material layer in which the hardly stretchable polymer part forming material is arranged at a predetermined site. The process which obtains the extensible organic base material in which the difficulty extensible polymer part was partially and integrally formed in the easily extensible polymer base material by performing two treatments

  First, in step A, a solution or dispersion containing a liquid precursor of a polymer (a) and a weathering agent constituting the easily stretchable polymer matrix, and the polymer (a) and the weathering agent on the support. Alternatively, an easily stretchable polymer base material forming material layer is formed by a mixture of the polymer (a) alone and a weathering agent.

  In step A, the support is not particularly limited, and for example, a separator can be used. The separator is not particularly limited, and a conventional release paper, a separator having a release treatment layer, a low adhesive substrate made of a fluoropolymer, a low adhesive substrate made of a nonpolar polymer, and the like can be used. Examples of the separator having the release treatment layer include a plastic film or paper surface-treated with a release treatment agent such as silicone-based, long-chain alkyl-based, fluorine-based, or molybdenum sulfide. Examples of the fluorine-based polymer in the low adhesion substrate made of the above-mentioned fluoropolymer include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chloro Examples include fluoroethylene-vinylidene fluoride copolymer. Moreover, as said nonpolar polymer, olefin resin (for example, polyethylene, a polypropylene, etc.) etc. are mentioned, for example. The separator can be manufactured by a known or conventional method. Further, the thickness of the separator is not particularly limited.

  Examples of the liquid precursor of the polymer (a) constituting the easily stretchable polymer matrix include monomers (energy ray-curable monomers and the like) that can be derived into the polymer (a), partial polymers of the monomers, polymers by curing or crosslinking ( Examples thereof include a polymer that can be derived into a), a polymer before curing or crosslinking. A mixture thereof may be used. As the solution or dispersion containing the polymer (a) and the weathering agent, a composition obtained by adding a weathering agent to an aqueous solution or an organic solvent solution of the polymer (a), an aqueous dispersion containing the polymer (a) and the weathering agent, An organic solvent dispersion liquid is mentioned. As the solvent, those exemplified in the above section [Easily stretchable polymer matrix] can be used.

  For forming a stretchable polymer base material by using a liquid mixture of the liquid precursor of the polymer (a) and the weathering agent constituting the stretchable polymer matrix or a solution or dispersion containing the polymer (a) and the weathering agent. In the case of forming the material layer, for example, an easily stretchable polymer base material forming material layer can be formed by coating them on a support. The viscosity of the coating liquid is, for example, 0.1 to 50 Pa · s at a coating temperature (for example, a predetermined temperature within a range of 10 to 40 ° C., particularly 25 ° C.) from the viewpoint of workability and the like. The upper limit is preferably 30 Pa · s, more preferably 20 Pa · s, and the lower limit is preferably 0.5 Pa · s, more preferably 1 Pa · s. If the viscosity is too low, the shape tends to be difficult to maintain. Conversely, if the viscosity is too high, the coating workability tends to decrease.

  The coating method is not particularly limited, and for example, a coater such as a Meyer bar, a blade coater, an air knife coater, a roll coater, a die coater, an extruder, a printing machine, or the like can be used.

  When the easily stretchable polymer base material forming material layer is formed by a mixture of the polymer (a) alone and the weathering agent, for example, a predetermined amount of the polymer (a) alone and the weathering agent are formed on the support. An easily stretchable polymer base material forming material layer can be formed by placing the mixture, placing a support (separator or the like) on the mixture, and pressing it under heating (at a temperature equal to or higher than the melting temperature of the polymer). Moreover, the easily extensible polymer base material forming material layer can be formed on the support by extruding a mixture of the polymer (a) and the weathering agent. Furthermore, using a mixture of the polymer (a) and the weathering agent, a layer to be a material layer for forming an easily extensible polymer base material is prepared separately by an appropriate molding method, and this is transferred onto a support. Thus, an easily stretchable polymer base material forming material layer can be formed.

  In addition, formation of the easily extensible polymer base material forming material layer can also be performed using an appropriate mold. In this case, the viscosity of the forming material may be lower than the above range.

  The thickness of the easily stretchable polymer base material forming material layer is, for example, 0.01 mm to 1 cm, and the upper limit is preferably 5 mm, more preferably 2 mm, and the lower limit is preferably 0.03 mm. Preferably it is 0.05 mm.

  Next, in the process B, the hardly extensible polymer part forming material is disposed at a predetermined portion of the easily extensible polymer base material forming material layer. The material for forming a hardly extensible polymer portion may be any of solid, liquid, gas, solution, dispersion and the like. As the material for forming the hardly extensible polymer part, a material (polymer material) (b) precursor constituting the hardly extensible polymer part (for example, an energy ray curable composition), a material constituting the hardly extensible polymer part (Polymer material) (b) itself may be a solution or dispersion containing the material (polymer material) (b) constituting the hardly extensible polymer part. If necessary, the weather resistance agent can be added to the material for forming a hardly extensible polymer part.

  In step B, as the material for forming the hardly extensible polymer part, the hardly extensible polymer part is composed of the structural unit derived from the monomer (i) whose Tg of the homopolymer is 5 ° C. or more with respect to all the structural units of the polymer. The monomer component containing 50% by weight or more of the monomer having a Tg of 5 ° C. or higher, or a partial polymer thereof. A curable composition (such as an energy beam curable composition) can be used. This curable composition usually contains a polymerization initiator.

  A polymer material containing a polymer containing 50% by weight or more of a structural unit derived from a polyfunctional monomer having (ii) two or more curable groups in the molecule, based on the total structural unit of the polymer. In the case of constituting, a curable composition containing a monomer component containing 50% by weight or more of a polyfunctional monomer having two or more of the curable groups in the molecule, or a partially polymerized product thereof as a material for forming a hardly extensible polymer part A product (such as an energy beam curable composition) can be used. This curable composition usually contains a polymerization initiator.

  When the hardly extensible polymer part is composed of the above-mentioned (iii) filler-containing polymer material, as the hardly extensible polymer part forming material, a dispersion containing a filler (an aqueous dispersion, an organic solvent dispersion, etc.), A curable composition comprising the filler and a monomer (such as an energy ray-curable monomer) that can be derived into a polymer that should constitute the hardly extensible polymer part or a partial polymer thereof, and a filler and the hardly extensible polymer part A mixed liquid of a polymer before curing or crosslinking that can be induced by curing or crosslinking and a crosslinking agent, or a filler alone (powder) can be used.

  When the hardly extensible polymer part is composed of (iv) a polymer material having a tensile elastic modulus of 0.1 MPa or more, the polymer having the tensile elastic modulus of 0.1 MPa or more is used as the hardly extensible polymer part forming material. A curable composition containing an inducible monomer (such as an energy beam curable monomer) or a partial polymer thereof (such as an energy beam curable composition) can be used.

  A method (means) for disposing the hardly extensible polymer part forming material at a predetermined portion of the easily extensible polymer base material forming material layer is not particularly limited. For example, (1) forming the hardly extensible polymer part The material for coating, dripping, and mounting is applied from above to a predetermined portion of the material layer for forming an easily stretchable polymer base material so that the surface shape of the difficultly stretchable polymer portion or the projected shape of the substrate surface is a desired shape. A method of placing, driving or printing; (2) the surface shape of the hardly extensible polymer portion or the material for forming the hardly extensible polymer portion in a liquid form at a predetermined position of the easily extensible polymer base material forming material layer; A method of injecting so that the projected shape of the substrate surface becomes a desired shape, and (3) a hardly extensible polymer on a support different from the support on which the material layer for forming the easily extensible polymer base material is formed. The material used to form the part is the surface shape or As the substrate surface projected shape has a desired shape, coating, dripping, placing 置又 prints, and a method of transferring it to the easily extensible polymer matrix forming material layer.

  When the hardly extensible polymer part forming material is in a liquid state, the viscosity of the liquid is a temperature at the time of coating, dripping, etc. from the viewpoint of workability and the like (for example, a predetermined temperature within a range of 10 to 40 ° C. In particular, at 25 ° C., for example, 10 to 50000 mPa · s, the upper limit is preferably 30000 mPa · s, more preferably 20000 mPa · s, and the lower limit is preferably 20 mPa · s, more preferably 30 mPa · s. s. If the viscosity is too low, it becomes difficult to obtain a difficult-extensible polymer portion having a desired shape. Conversely, if the viscosity is too high, the coating workability tends to be lowered.

  Coating, dripping, mounting, driving, printing, pouring, and transfer are not particularly limited, and can be performed by known or conventional methods. For example, an appropriate dropping device can be used for dropping, and a syringe or the like can be used for injection. Examples of printing include screen printing.

  By selecting and adjusting the kind, amount of use, viscosity, etc., of the hardly extensible polymer portion forming material disposed at a predetermined site of the easily extensible polymer base material forming material layer, the size of the hardly extensible polymer portion ( The size and height in the surface direction can be controlled. In the case of forming a plurality of hardly extensible polymer parts, the hardly extensible polymer part forming material is applied at an appropriate interval. In addition, the shape of a hardly extensible polymer part is controllable by using the means which regulates the dripping and injection | pouring location of the material for forming a hardly extensible polymer part. The drop method is often used when the size of the hardly extensible polymer portion is relatively large, and the injection method is often used when the size of the hardly extensible polymer portion is relatively small. In the case of the dropping method, there is an advantage that the tip of the dropping device does not come into contact with the material for forming an easily stretchable polymer base material, so that it does not get dirty. In the case of the injection method, there is an advantage that the hardly extensible polymer part forming material is less likely to diffuse into the easily extensible polymer base material forming material layer than the dropping method.

  In addition, when using the energy-beam curable composition which is a precursor of the material (b) which comprises a difficult-to-extend polymer part as a material for forming a hardly-extensible polymer part, this energy-ray-curable composition (application | coating) Liquid) at the predetermined site of the easily stretchable polymer base material forming material layer, the energy ray curable composition (coating liquid) diffuses to the periphery (the easily stretchable polymer base material forming material layer). In order to suppress, it is preferable to contain a polymer in the energy beam curable composition. In particular, when a large number of hardly extensible polymer parts are formed in the easily extensible polymer base material, after a predetermined number of coating liquids are arranged in a predetermined part of the easily extensible polymer base material forming material layer, energy rays are applied. When moving to the irradiation process, the coating solution diffuses to the peripheral part (bleeds) over time at the place where the coating solution is initially placed, and cures in that state, and is difficult to stretch in the desired shape and size. A polymer part may not be obtained or the outline of a difficult-to-extend polymer part may become unclear. In such a case, if a polymer is contained in the energy beam curable composition (coating liquid), the monomer and the like contained in the coating liquid are in the periphery (material layer for forming an easily extensible polymer base material). ), And even when a large number of hardly extensible polymer portions are formed, it is possible to form a hardly extensible polymer portion having a uniform shape and size and having a clear outline. This method provides a great diffusion suppressing effect particularly when the energy beam curable composition (coating liquid) is disposed by dropping at a plurality of predetermined sites of the easily stretchable polymer base material forming material layer.

  Although it does not specifically limit as a weight average molecular weight of the polymer mix | blended in the said energy-beam curable composition, For example, it is 1000 or more, Preferably it is 2000 or more, More preferably, it is 3000 or more. If the weight average molecular weight of the polymer is too low, the diffusion suppressing effect tends to be small. On the other hand, if the weight average molecular weight of the polymer is too large, the viscosity of the composition (coating solution) becomes too high, and the coating workability may be reduced. From this viewpoint, the upper limit of the weight average molecular weight of the polymer is, for example, 5000000, preferably 1000000, and more preferably 100,000. The polymer content in the energy ray-curable composition (coating liquid) is, for example, 5% by weight or more, preferably 10% by weight or more, and more preferably 20% by weight or more. When the polymer content is less than 5% by weight, the diffusion suppressing effect is small. Moreover, when there is too much content of a polymer, the viscosity of an energy-beam curable composition (coating liquid) will become high too much, and coating workability | operativity will fall easily. From this viewpoint, the upper limit of the content of the polymer in the energy beam curable composition (coating liquid) is, for example, 95% by weight, preferably 90% by weight, and more preferably 85% by weight.

  The polymer blended in the energy ray curable composition is not particularly limited as long as it does not impair the physical properties (characteristics) required for the hardly extensible polymer portion, and constitutes the easily extensible polymer base material. Any of the polymer exemplified as the polymer and the polymer exemplified as the polymer constituting the hardly extensible polymer portion may be used, but the integrity of the easily extensible polymer base material and the hardly extensible polymer portion, adhesion, etc. From the viewpoint, the same type of polymer as the polymer constituting the easily stretchable polymer matrix, or the same polymer chain as the polymer chain (main chain or side chain) of the polymer constituting the easily stretchable polymer matrix A polymer having a chain is preferred.

  As the energy ray curable composition (coating liquid), the easy-extensible polymer matrix 60 seconds after dropping the coating liquid onto the material layer for forming an easily extensible polymer matrix (drop amount 0.03 μL). The diameter of the coating solution on the material forming material layer is preferably 1.2 times or less, more preferably 1.15 times or less than the diameter of the coating solution immediately after dropping. In addition, the diameter of the coating liquid on the easily stretchable polymer base material forming material layer 120 seconds after dropping the coating liquid on the easily stretchable polymer base material forming material layer (drop amount 0.03 μL) is Those that are 1.4 times or less the diameter of the coating solution immediately after dropping are preferred, and those that are 1.3 times or less are more preferred. From a coating solution in which the diameter of the coating solution after 60 seconds or 120 seconds after dropping is larger than the diameter of the coating solution immediately after dropping, a pattern sheet [easily stretchable polymer base material] In some cases, an extensible organic base material in which a number of hardly extensible polymer portions are formed (for example, formed in a regular pattern) may not be obtained.

  After coating, dripping, placing, driving in, printing, pouring or transferring the material for forming an inextensible polymer part, the material for forming an inextensible polymer part is a material for forming an easily extensible polymer base material as required. Let stand until it penetrates, migrates and settles to the desired depth of the layer.

  Then, in step C, the reaction, solvent drying and removal treatment, and the melting / cooling treatment (hot melt) are performed on the easily stretchable polymer base material forming material layer in which the hardly stretchable polymer portion forming material is arranged at a predetermined site. At least one treatment selected from (Treatment) is performed to obtain an extensible organic base material in which the hardly extensible polymer portion is partially and integrally formed in the easily extensible polymer base material.

  Examples of the reaction include a polymerization reaction by energy rays and heat, curing, or a crosslinking reaction. The solvent is removed by drying at an appropriate temperature according to the type of the solvent. The solvent may be removed by drying at normal pressure or under reduced pressure. The melting is preferably performed at a temperature at which both the easily stretchable polymer base material forming material layer and the hardly stretchable polymer part forming material are melted.

  In the present invention, the combination of the form of the easily extensible polymer base material forming material used in step A and the form of the hardly extensible polymer part forming material used in step B is not particularly limited and can be arbitrarily combined. . For example, when an energy ray curable material [liquid precursor of polymer (a) (syrup or the like)] is used as the material for forming an easily stretchable polymer base material, a solvent-based material [solution containing polymer (a)] is used. In the case of using a dispersion-based material [emulsion containing polymer (a), etc.] or a case of using a hot-melt material [polymer (a) alone], the hardly extensible polymer part forming material may be a solvent. Materials (polymer solutions), dispersion materials (polymer emulsions, etc.), energy ray curable materials [polymeric liquid precursors (syrups, etc.)], solids [hot melt materials (polymer alone), fillers (powder) Etc.] can be used. More specifically, the form of the easily stretchable polymer base material and the hardly stretchable polymer part forming material is a combination of energy ray curable materials (energy ray curable syrups, etc.), solvent-based materials Combinations of (solutions), dispersion materials (emulsions, etc.), hot melt materials, and combinations of solvent materials (solutions) and dispersion materials (emulsions, etc.) (in no particular order) ), Combinations of hot-melt materials and solvent-based materials (solutions) (in no particular order), combinations of hot-melt materials and dispersion-based materials (emulsions, etc.) (in no particular order), solvent-based materials (solutions) and fillers Any of a combination of (powder), a dispersion material (emulsion, etc.) and a filler (powder), a hot melt material and a filler (powder), etc. may be used. In step C, by performing a treatment suitable for the form of each material, an extensible organic base material in which the hardly extensible polymer portion is partially and integrally formed in the easily extensible polymer base material is obtained. Can do.

  In addition, in the vicinity of the interface between the hardly extensible polymer portion and the easily extensible polymer base material portion, the extensible organic base material having a gradation regarding the composition and / or physical properties (elongation characteristics, hardness, etc.) is, for example, easily extensible. Manufactured by using materials that are common or similar to each other (solvents, monomers, etc.) or materials that are compatible with each other (solvents, monomers, etc.) can do. Specifically, for example, by forming both the easily stretchable polymer base material forming material and the hardly stretchable polymer part forming material with a material (such as a polymer liquid precursor) containing an acrylic monomer, A gradation can be obtained. Such gradation is formed by diffusion and migration of monomer components, solvents, and the like, and subsequent curing, solvent removal, and the like. Therefore, the gradation part of the extensible organic base material having the gradation is different from the composition assumed from the material for forming each part [hardly extensible polymer part, easy extensible polymer base material part]. The degree of gradation (width) can be adjusted by the type and amount of the easily stretchable polymer base material forming material and the hardly stretchable polymer part forming material (solvent, monomer, etc.). Further, as described above, in the case of using an energy ray curable composition as the material for forming a hardly extensible polymer part, when a polymer is blended in the energy ray curable composition, the type and amount of the polymer The gradation level (width) can be adjusted by the weight average molecular weight or the like.

  In the present invention, the following modes (I) to (III) are preferable as a method for producing a sheet-like organic substrate having extensibility from the viewpoint of efficient production.

  (I) In step A, an easily extensible polymer base material forming material layer is formed on a support by a mixed solution of an energy ray curable composition which is a liquid precursor of the polymer (a) and a weathering agent. In Step B, an energy ray curable composition that is a precursor of the material (b) constituting the hardly extensible polymer portion is disposed at a predetermined portion of the easily extensible polymer base material forming material layer, and Step C The energy ray curable composition which is the precursor of the material (b) is irradiated with energy rays on the easily stretchable polymer base material forming material layer arranged at a predetermined site, and the two energy ray curable compositions are used. Is a method of obtaining a sheet-like organic base material having extensibility in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer base material.

  (II) In step A, an easily extensible polymer base material forming material layer is formed on the support with a solution or dispersion containing the polymer (a) and a weathering agent. In step B, the easily extensible polymer is formed. A material (b) [for example, polymer, filler (powder), etc.] constituting the hardly extensible polymer part or a solution or dispersion containing the material (b) is disposed at a predetermined portion of the base material forming material layer. In the step C, the material (b) constituting the hardly extensible polymer part or the easily extensible polymer base material forming material layer in which the solution or dispersion containing the material (b) is arranged at a predetermined site, A method for obtaining a sheet-like organic base material having extensibility in which a hardly extensible polymer portion is partially and integrally formed in an easily extensible polymer base material by performing a drying removal treatment.

  (III) In step A, an easily extensible polymer base material forming material layer is formed on the support by a mixture of the polymer (a) alone and a weathering agent, and in step B, the easily extensible polymer base material is formed. Material (b) [for example, polymer, filler (powder), etc.] constituting the hardly extensible polymer portion is arranged at a predetermined portion of the forming material layer, and in step C, the material constituting the hardly extensible polymer portion The material layer for forming an easily stretchable polymer base material in which (b) is arranged at a predetermined site is subjected to a melting / cooling treatment (hot melt treatment) to form a hardly stretchable polymer in the easily stretchable polymer base material (A). A method for obtaining a sheet-like organic substrate having extensibility, in which parts are partially and integrally formed.

More specifically, the sheet-like organic base material having extensibility in the present invention can be produced, for example, through the following steps.
Step A1: Step of forming an easily extensible polymer matrix-forming energy beam curable composition layer on a support Step B1: In a predetermined part of the easily extensible polymer matrix-forming energy beam curable composition layer, A step of arranging (containing) the energy ray-curable composition for forming a hardly-extensible polymer portion so that the surface shape of the hardly-extensible polymer portion or the projected surface shape of the base material has a desired shape Step C1: The above-mentioned difficult extension An energy beam curable composition for forming a hardly extensible polymer part is formed by irradiating an energy ray curable composition layer for forming an easily extensible polymer matrix with an energy ray curable composition for forming an extensible polymer part. Extensibility in which the hardly extensible polymer portion is partially and integrally formed in the easily extensible polymer matrix by curing the material and the energy ray curable composition layer for forming the easily extensible polymer matrix Obtaining a sheet-shaped organic substrate having

  This method is a specific example of the embodiment (I), and FIG. 3 is a schematic explanatory view (cross-sectional view) thereof. In FIG. 3, (a) is a process A1, (b) is a process B1, (c), (d), (e), (f) [or (d '), (e'), (f)] Corresponds to step C1.

  In step A1, the energy-beam curable composition layer 20 for forming an easily extensible polymer base material is formed on the support 4. As the support 4, those described above can be used.

The energy-extensible curable composition layer 20 for forming an easily stretchable polymer base material includes, for example, the polyurethane chain, polyurea chain, polyurethane urea chain, polyolefin chain (particularly, polydiene chain), silicone chain, polyester chain, and polyether. A curable polymer P having at least one polymer chain selected from the group consisting of a chain, a polyamide chain, a polystyrene polymer chain, and a polyacryl chain, and having an energy ray-curable group A ₁ in the main chain or side chain An energy beam curable composition comprising a mixture of a curable polymer P and a curable monomer P having an energy beam curable group A ₂ and a weathering agent, and a photopolymerization initiator. It can be formed by coating on top.

  A solvent may be added to the curable composition as necessary, but it is preferable not to use a solvent because a process for removing the solvent later increases. Moreover, in order to prevent the superposition | polymerization by a heat | fever, you may add a polymerization inhibitor to the said curable composition as needed.

  The curable composition is preferably in the form of a syrup. The viscosity of the curable composition and the coating method are the same as described above. In addition, formation of the energy-beam curable composition layer 20 for easily extensible polymer base material formation can also be performed using a suitable type | mold. In this case, the viscosity of the curable composition may be lower than the above range.

  The thickness of the easily extensible polymer base material forming energy beam curable composition layer 20 is the same as described above.

  In step B1, the energy ray-curable composition 30 for forming a hardly extensible polymer part is disposed (included) in the energy ray-curable composition layer 20 for forming an easily extensible polymer base material.

  In the step B1, for example, a monomer [particularly, a (meth) acrylic monomer] having a Tg of the homopolymer of 5 ° C. or higher (more preferably 15 ° C. or higher, more preferably 50 ° C. or higher) is 50% by weight or more (more A monomer component containing preferably 60% by weight or more, more preferably 80% by weight or more, or a polyfunctional monomer having two or more curable groups in the molecule is 50% by weight or more (more preferably 60% by weight or more, more preferably 80% by weight or more) An energy ray-curable composition containing a monomer component and a photopolymerization initiator is added to a predetermined portion of the easily extensible polymer base material forming energy ray-curable composition layer 20 from above. (Dropping) or by injecting into a predetermined location in the energy-beam curable composition layer 20 for forming the easily stretchable polymer base material. That. Also, transfer onto the energy ray curable composition layer 20 for forming an easily extensible polymer base material from a support on which an energy ray curable composition containing the monomer component and a photopolymerization initiator is coated and dropped. Can also be done.

  It is preferable that the energy ray-curable composition 30 for forming a hardly extensible polymer part is in a syrup shape. From the viewpoint of workability and the like, the viscosity of the energy-beam curable composition 30 for forming a hardly extensible polymer part is a temperature at the time of coating (for example, a predetermined temperature within a range of 10 to 40 ° C, particularly 25 ° C). For example, the upper limit is preferably 30000 mPa · s, more preferably 20000 mPa · s, and the lower limit is preferably 20 mPa · s, more preferably 30 mPa · s. If the viscosity is too low, it is difficult to obtain a desired shape. Conversely, if the viscosity is too high, the coating workability tends to be lowered.

  The addition and injection method of the energy ray-curable composition 30 for forming a hardly extensible polymer part is not particularly limited, and for example, a syringe, an appropriate dropping device, and the like can be used. Moreover, the transfer method of the energy ray-curable composition 30 for forming a hardly extensible polymer portion is not particularly limited. For example, a method using an intaglio coating machine such as a gravure coater, energy ray curable for forming a hardly extensible polymer portion. The support etc. which apply | coated and dripped the composition 30 and the method of bonding the energy-beam curable composition layer 20 for extensible polymer base material formation etc. can be used.

  By adjusting the amount and viscosity of the energy ray-curable composition 30 for forming a hardly extensible polymer part, the size (size and height in the plane direction) of the hardly extensible polymer part 3 after curing can be controlled. . When a plurality of the hardly extensible polymer portions 3 are formed, the energy ray curable composition 30 for forming the hardly extensible polymer portions is applied at an appropriate interval. In addition, the shape of the hard-extensible polymer part 3 after hardening is controllable by using the means which regulates the addition or injection | pouring location of the energy beam curable composition 30 for hard-extensible polymer part formation.

  In step C1, the energy beam curable composition layer 20 for forming an easily extensible polymer matrix containing the hardly extensible polymer portion forming energy beam curable composition 30 is irradiated with an energy beam, and the difficult elongation is achieved. The energy ray-curable composition 30 for forming the extensible polymer part and the energy ray-curable composition layer 20 for forming the easily extensible polymer base material are cured, and the hardly extensible polymer part 3 is part of the easily extensible polymer base material 2. A sheet-like organic substrate having extensibility formed integrally and integrally is obtained.

  Although ultraviolet rays (UV) are used as energy rays in FIG. 3, ionizing radiation such as α rays, β rays, γ rays, neutron rays, electron rays, and visible rays may be used as described above.

  The irradiation energy, irradiation time, irradiation method, and the like of the energy beam are not particularly limited as long as the photopolymerization initiator can be activated to cause the monomer component to react.

  As the energy beam irradiation device, a conventional device can be used. For example, when irradiating ultraviolet rays, a mercury lamp, a fluorescent lamp, a sodium lamp, a metal halide lamp, a xenon lamp, a neon tube, a neon lamp, a high-intensity discharge lamp, or the like can be used.

  An easily extensible polymer base material containing the hardly extensible polymer portion forming energy ray curable composition 30 for the purpose of preventing curing inhibition by oxygen during the irradiation of energy rays or for the purpose of smoothing the surface. The cover film 5 may be laminated on the surface of the forming energy beam curable composition layer 20. As the cover film 5, the same separator as the support 4 can be used. Lamination | stacking of the cover film 5 can be performed using a hand roller etc., for example.

Energy beam irradiation may be performed in several stages. For example, in the case of irradiating ultraviolet rays, as shown in FIG. 3 (c), irradiation is performed for a short time (for example, an integrated irradiation amount of 10 to 1000 mJ / cm ² ) at a high illuminance (for example, 50 to 1000 mW / cm ² ). After that, as shown in FIG. 3D, the cover film 5 is laminated, and thereafter, as shown in FIG. 3E, the cover film 5 is long at a low illuminance (for example, 1 to 40 mW / cm ² ). You may irradiate with time (for example, integrated irradiation amount 500-10000mJ / cm < ² >). Thus, the workability at the time of lamination | stacking of the cover film 5 by a hand roller can be improved by irradiating energy beam irradiation in several steps. In the figure, 200 is a partially cured energy beam curable composition layer for forming an easily extensible polymer base material, and 300 is a partially cured energy beam curable composition for forming an inextensible polymer portion.

In the case where the energy beam irradiation is performed in one stage, for example, after the step B1, as shown in FIG. 3 (d ′), the energy beam curable composition 30 for forming a hardly extensible polymer portion is contained. The cover film 5 may be laminated on the surface of the energy ray curable composition layer 20 for forming an easily stretchable polymer base material, and irradiated with ultraviolet rays as shown in FIG. Illuminance of ultraviolet in this case, for example 1~40mW / cm ^2, integrated dose is, for example, 500~10000mJ / cm ^2.

  After curing the hardly extensible polymer part forming energy beam curable composition 30 and the easily extensible polymer matrix forming energy beam curable composition layer 20 as described above, it is shown in FIG. As necessary, the cover film 5 and the support 4 are peeled off as necessary, and cut into an appropriate size as necessary, and used as the extensible organic substrate 1. The cutting operation may be performed before the cover film 5 or the support 4 is peeled off.

Moreover, the sheet-like organic base material which has the extendibility in this invention can also be manufactured by passing through the following process more specifically.
Step A2: Step of forming a stretchable polymer base material forming material layer by applying a solution or dispersion containing the polymer a constituting the stretchable polymer base material and a weathering agent on the support. A solution or dispersion containing a polymer constituting the hardly extensible polymer part or a filler (powder) constituting the hardly extensible polymer part is difficult at a predetermined part of the material layer for forming the easily extensible polymer base material. Step C2: The step of forming the hard-to-extend polymer so that the surface shape of the extensible polymer portion or the projected surface shape of the base material has a desired shape by coating, dripping, placing, driving in, printing, etc. Drying the stretchable polymer base material-forming material layer in which the solution or dispersion containing the polymer constituting the part, or the filler (powder) constituting the hardly stretchable polymer part is disposed, and removing the solvent; Easy stretchability Step hardly extensible polymer portion Rimmer base material to obtain a partially and sheet-like organic substrate having an integrally formed extensibility

  This method is a specific example of the embodiment (II), and FIG. 4 is a schematic explanatory view (cross-sectional view) thereof. In FIG. 4, (g) corresponds to step A2, (h) corresponds to step B2, and (i) and (j) correspond to step C2. Reference numeral 21 denotes a layer (material layer for forming an easily extensible polymer base material) composed of a solution or dispersion containing a polymer constituting the easily extensible polymer matrix and a weather resistance agent, and reference numeral 31 denotes a polymer constituting the hardly extensible polymer portion. The filler (powder) which comprises the solution or dispersion liquid containing this, or a hardly extensible polymer part is shown. Reference numerals 1, 2, 3, and 4 are the same as described above.

Furthermore, the sheet-like organic base material having extensibility according to the present invention can be more specifically manufactured through the following steps.
Step A3: Form a material layer for forming a stretchable polymer base material by forming a sheet of a mixture of the polymer a and the weathering agent constituting the stretchable polymer base material on a support by hot pressing, extrusion molding, or the like. Step Step B3: A polymer or filler (powder) constituting the hardly extensible polymer portion is applied to a predetermined portion of the easily extensible polymer base material forming material layer, and the surface shape of the hardly extensible polymer portion or the substrate surface projection. Step of placing (containing) by placing or dropping (melt) or the like so that the shape becomes a desired shape Step C3: Easy placement of polymer or filler (powder) constituting the hardly extensible polymer part An extensible sheet-like organic material in which a stretchable polymer base material forming material layer is heated and melted, and then cooled to form a stretchable polymer base material in which a hardly extensible polymer portion is partially and integrally formed. Get substrate Degree

  This method is a specific example of the above-described embodiment (III), and FIG. 5 is a schematic explanatory view (cross-sectional view) thereof. In FIG. 5, (k) corresponds to the process A3, (l) corresponds to the process B3, (m), and (n) corresponds to the process C3. Reference numeral 22 denotes a sheet (material layer for forming an easily extensible polymer base material) made of a polymer constituting the easily extensible polymer base material, and reference numeral 32 denotes a polymer or filler (powder) constituting the hardly extensible polymer portion. Reference numerals 1, 2, 3, and 4 are the same as described above.

  The extensible organic base material 1 thus obtained is a member for an electronic product (transistor, integrated circuit, capacitor, sensor, actuator, etc.) as an extensible member having a shape-invariant portion (or a stretchable member having a shape-invariant portion). , Members for optical products (displays, lighting, optical waveguide circuits, etc.), members for optoelectronic products (light emitting diodes, photodiodes, solar cells, etc.), members for car electronics products, members for home appliances, members for housing equipment, building materials , Band members, binding members, sanitary goods, clothing parts, poultice base fabrics, and the like.

  Further, in the extensible organic base material, when the surface shape of the difficult-to-extend part or the projected surface shape of the base material is linear, the extension part in the specific direction can be suppressed by the difficult-to-extend part. It can be used for a taping base material, a medical wound covering base material, a member that requires followability (workability) to a specific shape, and the like. Furthermore, since strength in a specific direction can be imparted, it can be used as a base material for seam joining (for example, a car, an airplane, etc.). Furthermore, since the elongation can be concentrated at a specific portion, it can be used as a dicing tape that can be efficiently extracted. Moreover, since the handleability of a thin film base material can be improved, it can utilize for a medical thin film base material (film dressing) etc. Furthermore, since an adherend can be strengthened, it can be utilized as a reinforcing member (glass cloth substitute) for a resin plate or a steel plate. Moreover, it can utilize as a shrink film which tracks a shape with a heat | fever by mix | blending a shape memory polymer with a difficulty extending | stretching part.

  Furthermore, when the difficultly stretched portion is continuously formed (penetrated) from one surface of the stretchable organic substrate to the other surface, and the difficultly stretched portion contains a conductive filler, For example, it can be used as an anisotropic conductive sheet, a dicing tape capable of conducting an on-chip conduction test, and the like. Furthermore, when the difficultly stretched portion is continuously formed (penetrated) from one surface of the stretchable organic substrate to the other surface, and the difficultly stretched portion contains a heat conductive filler Can be used, for example, as a heat transfer sheet that can be expanded or contracted.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited at all by these.

Production Example 1 (Manufacture of base material syrup A)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, 80 parts by weight of isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) as a (meth) acrylic monomer, n -20 parts by weight of butyl acrylate (BA, manufactured by Toa Gosei Co., Ltd.), 68.4 parts by weight of poly (oxytetramethylene) glycol (PTMG650, manufactured by Mitsubishi Chemical Corporation) having a number average molecular weight of 650 as a polyol, As a catalyst, 0.01 part by weight of dibutyltin dilaurate (DBTL) was added, and 25.5 parts by weight of hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) was added dropwise with stirring. It was made to react for a time and the urethane polymer-acrylic-type monomer mixture was obtained. Thereafter, 6.1 parts by weight of hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.) was further added and reacted at 65 ° C. for 1 hour, whereby an acryloyl group-terminated urethane polymer-acrylic monomer mixture. Got. Thereafter, the base material syrup A was added by adding 0.15 parts by weight of 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651”, manufactured by BASF) as a photopolymerization initiator. Got.

Production Example 2 (Manufacture of base material syrup B)
With respect to 100 parts by weight of the base material syrup A obtained in Production Example 1, 1.25 parts by weight of an antioxidant (trade name “TINUVIN123”, manufactured by BASF) and an ultraviolet absorber (trade name “TINUVIN400”, BASF) A base material syrup B was obtained by adding 0.6 parts by weight of the product and mixing uniformly.

Production Example 3 (Manufacture of syrup A for forming a hardly extensible polymer part)
100 parts by weight of trimethylolpropane EO-added triacrylate (trade name “Biscoat # 360”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and blue dye (trade name “SZ7620”, manufactured by Dainichi Seika Kogyo Co., Ltd.) 1 part by weight and 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651” 0.1 parts by weight as a photoinitiator were added and dispersed, and an acrylic monomer mixture (difficult A syrup A) for forming an extensible polymer part was obtained.

Production Example 4 (Manufacture of syrup B for forming a hardly extensible polymer part)
1.25 parts by weight of an antioxidant (trade name “TINUVIN123”, manufactured by BASF) and an ultraviolet absorber (trade name) with respect to 100 parts by weight of the syrup A for forming a hardly extensible polymer part obtained in Production Example 3. By adding 0.6 parts by weight of “TINUVIN400” (manufactured by BASF) and mixing them uniformly, an acrylic monomer mixture (syrup B for forming a hardly extensible polymer part) was obtained.

Example 1
The base material syrup B obtained in Production Example 2 was applied to the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) using an applicator, and a base material syrup layer having a thickness of 300 μm was formed. Formed. To a predetermined part of the base material syrup layer (at intervals of 30 mm in the longitudinal direction), from above, the hardly extensible polymer part forming syrup B (about 0.01 g) obtained in Production Example 4 is dropped to form island-shaped difficulty. The stretchable polymer portion forming syrup portions were formed at 30 mm intervals (center-to-center distance) in the longitudinal direction. Then, from above, ultraviolet rays are pre-irradiated with a metal halide lamp (MHL) (illuminance: 200 mW / cm ² , integrated irradiation amount: 200 mJ / cm ² ), and the base material syrup and the refractory polymer part forming syrup are semi-cured. After that, a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted on a semi-cured syrup with a hand roller, and further irradiated with ultraviolet rays by an ultraviolet lamp (BL type) ( UV illuminance: 3.4 mW / cm ² , integrated irradiation amount: 2000 mJ / cm ² ), hardened base material syrup [= easily stretchable polymer base material (easily stretchable part)] Hardening part for forming part [= hardly stretchable polymer part (hardly stretchable part)] (diameter of about 8.6 mm) is arranged at a predetermined interval [30 mm spacing (distance between centers)]. Extendable organic substrate (thickness: 300 [mu] m) was obtained. As a result of microscopic observation of the cross section, in the obtained extensible organic base material, the hardly extensible polymer portion was continuously formed from one surface of the extensible organic base material to a depth of 2/3 or more. It was not formed until it reached the surface (embedded type).

Comparative Example 1
Except for changing the base material syrup B to the base material syrup A obtained in Production Example 1, and changing the hardly stretchable polymer part forming syrup B to the hardly stretchable polymer part forming syrup A obtained in Production Example 3, An extensible organic base material was obtained in the same manner as in Example 1.

<Weather resistance test>
The stretchable organic substrates of Examples and Comparative Examples were exposed to light of 90 mW / cm ² with a metal weather at 40 ° C. and a humidity of 98% for 100 hours. Tensile tests were performed on stretchable organic substrates before and after exposure. A sample of an extensible organic substrate (width 20 mm) is placed so that two hard-extensible polymer portions forming syrup cured portions (= hard-extensible polymer portions) are placed between chucks (50 mm) (two hard-extensible polymers). The center-to-center distance of the syrup cured part for forming the part is set at 30 mm, and the tensile test is performed by a tensile tester (trade name “Autograph AG-X 200N”, manufactured by Shimadzu Corporation) (temperature: 25 ° C., tensile speed: 200 mm / min), and the strength (MPa) and elongation (%) were measured.
A case where the strength and elongation after the exposure were 80% or more before the exposure was evaluated as ◯, a case where the strength and elongation were 60 to 80% were evaluated as Δ, and a case where the strength and elongation were 60% or less were evaluated as ×. The state of the sheet after exposure was also confirmed visually. The results are shown in Table 1.

<Measurement of elongation>
Tensile test was performed by placing samples of the stretchable organic base material obtained in Example 1 (width 20 mm with respect to the length direction) so that two or more hardly stretchable polymer portions can be inserted between the chucks (50 mm). Tensile test (Temperature: 25 ° C, Tensile speed: 200 mm / min) using a machine (trade name “Autograph AG-X 200N”, manufactured by Shimadzu Corporation), 50% elongation (150% of the original length) ) In the extension direction S ₁ (%) (average value) of the hardly extensible polymer part and the extension direction of the site other than the hardly extensible polymer part [easily extensible polymer base part (= easily extensible part)] The elongation rate S ₂ (%) (average value) of the rubber was measured, and the ratio (S ₂ / S ₁ ) and the difference (S ₂ -S ₁ ) (%) were calculated. When S ₁ = 0, S ₂ / S ₁ = ∞.
Elongation rate S ₁ (%) is determined by measuring the elongation-direction diameter of the hardly extensible polymer portion (substantially circular diameter on the substrate surface) before and after elongation, and the formula: {(length after elongation−length before elongation) Length) / (length before stretching)} × 100).
Elongation rate S ₂ (%) is marked with 6 marks in the extension direction of the part other than the hardly-extensible polymer part (easily-extensible polymer base material part), and the length between adjacent marks before and after extension. And calculated by the formula: {(length after stretching−length before stretching) / (length before stretching)} × 100).
As a result, S ₁ (%) = 4, S ₂ (%) = 76, (S ₂ / S ₁ ) = 19, and (S ₂ −S ₁ ) (%) = 72.
In addition, the extensible organic base material obtained in Example 1 also had stretchability.

1 extensible organic base material 2 extensible base material (part) [easily extensible polymer base material (part)]
20 Material layer for polymer matrix formation (energy ray curable composition layer for easily extensible polymer matrix formation)
DESCRIPTION OF SYMBOLS 21 Material layer for polymer base material formation 22 Material layer for polymer base material formation 200 Energy beam curable composition layer for partially extensible polymer base material formation 3 Hardly stretchable part (hard stretchable polymer part)
30 Difficult-to-extend polymer part forming material (energy-beam curable composition for forming inextensible polymer part)
31 material for forming a hardly extensible polymer portion 32 material for forming a hardly extensible polymer portion 300 energy ray curable composition for forming a partially extensible polymer portion that has been partially cured 4 support 5 cover film

Claims (12)

  An extensible organic base material in which difficultly stretchable parts are partially and integrally formed in an extensible base material, wherein the extensible base material contains a weathering agent.   The extensible organic base material according to claim 1, wherein the weathering agent is at least one selected from an ultraviolet absorber and an antioxidant.   The extensible organic group according to claim 1 or 2, wherein the hardly extensible portion is partially formed in the extensible base material with or without being exposed on at least one surface of the extensible organic base material. Wood.   The surface shape of the difficultly stretched part, or the projected shape when the surface of the stretchable organic substrate of the difficultly stretched part is the projection surface is a substantially circular shape, a substantially polygonal shape, an amorphous shape, or a shape or ring that represents a character, symbol or number The extensible organic base material according to claim 3, which is strip-shaped or linear.   The extensible organic base material according to any one of claims 1 to 4, wherein the length of the long axis in the surface direction of the difficult-to-extend part is 0.05 mm to 10 cm.   The extensible organic base material according to any one of claims 1 to 5, wherein a plurality of difficultly elongated portions are formed in a regular pattern in the extensible base material.   The extensible organic base material according to claim 6, wherein a distance between adjacent difficultly stretched portions is 0.05 mm to 50 cm.   The extensible organic substrate according to any one of claims 1 to 7, which has a thickness of 0.01 mm to 1 cm.   The extensible organic base material according to any one of claims 1 to 8, wherein a length in the thickness direction of the difficult extension part is at least 1/50 of the thickness of the extensible organic base material.   The extensible organic base material as described in any one of Claims 1-9 in which the difficult extension part is continuously formed from one surface of an extensible organic base material to the other surface.   The extensible organic base material according to any one of claims 1 to 10, wherein the elongation characteristic forms a gradation in the vicinity of the interface between the hardly elongated portion and the extensible base material.   Furthermore, the extensible organic base material as described in any one of Claims 1-11 which has a stretching property.

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