JP2002242085A - Bright composite film material having transparent textile weave - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a unique composite film material in which the textile weave of base fabric can be seen through, which has excellent color brightness. SOLUTION: This composite film material comprises the base fabric composed of a knitted and woven fabric having 10-60 L* value of brightness index and a bright surface resin coating layer comprising 0.5-10 pts.wt. of a pearl pigment (comprising 70-100 wt.% of a dichroic interference titanium mica therein) and a thermoplastic resin, having 25-85% light transmittance, and allowing the sight through of the textile weave. Filaments composing the base fabric may have mutually different L* values or the base fabric may be formed from a filament having 10-60 L* value and a filament having 61-98 L* value. The base fabric may have 15-40% porosity, further have a thermoplastic resin coating layer on the backside and have 5-45 L* value difference between the coating layers on the front and the backside.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film material which is capable of seeing through the knitting and weaving structure of a base fiber cloth, has a beautiful color, and has excellent glitter. More specifically, the present invention relates to a decorative film material that is suitably used for applications such as awning tents, covers, interior materials, decorative sheets, and other miscellaneous goods and uses as these members.

[0002]

2. Description of the Related Art Conventionally, awning tents, covers, interior materials,
In the field of decorative sheets and other synthetic resin leather for miscellaneous goods, various surface decoration techniques are provided to products. Among them, metallic pigments such as metal powder pigments (mainly aluminum powder pigments) and pearl (mica) pigments are dispersed in synthetic resins for the purpose of imparting a high-grade feel, or these metallic pigments are contained on the surface of leather. There are known techniques for performing a surface treatment using a paint to be applied or printing using an ink. In particular, pearl pigments provide a calm pearlescent appearance, so stationery, toys, sundries, packaging materials,
There is a great demand from a wide range of applications such as decorative boards, stickers, cosmetics, and automobiles. In addition, pearl pigments are widely used for white automobile body color coatings because of their excellent weather resistance. Recently, special color pearl pigments whose surface is coated with iron oxide have played a large role as a colorant that enhances the luxury of cars. In addition, special pearl pigments whose surface is coated with titanium oxide can produce a unique coloration that cannot be obtained with metal powder pigments, and thus demand in the cosmetics field such as lipsticks, eye shadows, and nail polish has been increasing as well as in the automobile field.

[0003] Usually, a synthetic resin leather or the like has a synthetic resin foamed layer (mainly a soft polyvinyl chloride resin) on one surface of a fiber base cloth and a synthetic resin (mainly a soft polyvinyl chloride resin) provided thereon. It is composed of a film layer.
Further, a tarpaulin such as a tent film material and a curing sheet is formed by adhering colored soft polyvinyl chloride resin film layers on both surfaces of a fiber base fabric. In the prior art, a pearlescent colored sheet is processed by using a pearl pigment and a surface-coated special pearl pigment for these synthetic resin (soft polyvinyl chloride resin) colored films. In particular, special pearl pigments, whose surface is coated with titanium oxide, have the property of causing interference colors depending on the hue of the underlying film layer on which a pigment used in combination with the pigment dispersed in the synthetic resin or a coating containing the pearl pigment is applied, for example, marking. In the field of films and stickers, a synthetic resin film containing a pearl pigment is laminated on the surface of a synthetic resin film colored with a chromatic pigment, or a paint containing a pearl pigment is applied on the surface of a synthetic resin film colored with a chromatic pigment. Coated ones have been proposed.

On the other hand, in a decorative sheet such as a synthetic resin leather or a tent, a fiber woven fabric is used as a base material in order to provide dimensional stability and strength according to the application. It is not preferable in terms of application that the woven fabric can be seen through the surface as it is. Therefore, these decorative sheets are usually surface-coated with a synthetic resin (mainly a soft polyvinyl chloride resin) and embossed to such an extent that the fiber fabric cannot be visually identified. Therefore, the special pearl pigment processing technology used in the fields of marking films and stickers described above can also be applied in the field of sheets such as synthetic resin leather and tarpaulins. It is possible to ask. By the way, in these applications, properties other than strength and dimensional stability are not required for the fiber woven fabric, and fiber yarns usually used for the fiber woven fabric are manufactured without coloring. In particular, synthetic fiber multifilaments (mainly PET fibers) excellent in cost and performance are widely used for fiber yarns of fiber woven fabrics used for applications such as synthetic resin leather and tents. Since this fiber yarn is a fiber bundle of ultrafine fiber filaments manufactured without coloring, it has a white appearance color by irregularly reflecting light.

On the other hand, as an example of utilizing the geometric repetition pattern of various woven structures of the fiber woven fabric itself for the design of products, a transparent colored synthetic resin (mainly a soft poly Although a laminate of a (vinyl chloride resin) film is known, the design is poor only with a geometrically repeated pattern of a woven structure. Therefore, for the purpose of imparting a more unique design, a method has been devised in which a metallic pigment such as a metal powder pigment or a pearl pigment is blended into these synthetic resin films to obtain a luminous geometrically repetitive pattern appearance. I have. Certainly, according to this method, a decorative sheet such as a synthetic resin leather or a tent having a glittering geometric repeating pattern appearance can be easily obtained.
When metal powder pigments (mainly aluminum powder pigments) are used, the resulting metallic feeling is too glaring and is not suitable for everyday use, and only small pieces are used as members of toys and miscellaneous goods. In the case of pearl pigments,
There is a drawback that a sufficient pearlescent appearance cannot be obtained unless a large amount of pearl pigment is blended due to insufficient hiding power. Therefore, in these applications, it is common to blend a metal powder pigment and a pearl pigment to adjust an arbitrary metallic appearance. However, in this case, due to the concealing property of the metal powder pigment used in combination, subtle appearances such as glossiness and hair lines of the fiber yarn of the fiber fabric are lost, and not only lack of three-dimensional appearance but also only monotonous metallic appearance is obtained. There are drawbacks.

[0006] In order to obtain a more individualized design, the above-mentioned attempt to use the special pearl pigment surface-coated with titanium oxide requires a special base hue. There is a contradictory problem that the appearance cannot be expressed. Accordingly, the knitting structure of the base fiber cloth is transparent, and at the same time, the sheet having a beautiful color and excellent brilliancy, and further, the knitting structure of the base fiber cloth is transparent, and at the same time, the color tone depends on the observation direction. No bright glittering sheet has been developed.

[0007]

SUMMARY OF THE INVENTION The present invention has a base fabric made of a fiber knitted and woven fabric, and a glitter resin coating layer formed on at least one surface of the base fabric.
It is possible to see through the glittering resin coating layer, and to provide a composite film material excellent in design, beautiful color, and glitter, and furthermore, it is possible to see through the knitting structure of the base fiber cloth. And at the same time, to provide a brilliant sheet whose color tone changes depending on the viewing direction.

[0008]

The present invention has been studied and studied in order to solve the above-mentioned problems. As a result, the present invention provides a glittering composite film material having a woven structure which can be seen through (1). A base fabric made of a fiber knitted fabric, and covering at least one surface of the base fabric,
And 100 parts by weight of a thermoplastic resin and 0.5 parts of a pearl pigment.
And a brilliant resin coating layer containing 10 to 10 parts by weight, and the fiber knitted and woven fabric for a base fabric is JIS Z-8729-198.
Lightness index L of the CIE1976 color system specified to 0
^{* The} pearl pigment has a value of 10 to 60, wherein the pearl pigment contains 70 to 100% by weight of the dichroic interference mica titanium, and the brilliant resin coating layer has a visible light transmittance of 25 to 85%. (JIS K-6714-1988), (2). A base fabric made of a fiber knitted fabric, and covering at least one surface of the base fabric, and having a glittering resin coating layer containing 100 parts by weight of a thermoplastic resin and 0.5 to 10 parts by weight of a pearl pigment. On the surface of the glittering resin coating layer, a glittering resin outermost layer is further formed, and the glittering resin outermost layer is based on 100 parts by weight of the thermoplastic resin.
The pearl pigment contained in the brilliant resin coating layer contains 0.5 to 10 parts by weight of a pearl pigment having a different interference color from the pearl pigment, and the fiber knitted and woven fabric for a base fabric has a lightness index L ^* value of a CIE1976 color system. 10 to 60, wherein the pearl pigment contains 70 to 100% by weight of the weight of the dichroic interference mica titanium, and the glittering resin coating layer on which the glittering resin outermost layer is formed is 25%. Having a visible light transmittance of ８５85%, (3). A base fabric made of a fiber knitted woven fabric, and at least one surface of the base fabric, a transparent and colored, or having a colorless thermoplastic resin coating layer, on the surface of the thermoplastic resin coating layer, A glittering resin outermost layer containing 0.5 to 10 parts by weight of a pearl pigment with respect to 100 parts by weight of the thermoplastic resin is further formed, and the fiber knitted and woven fabric for the base fabric has a lightness index L ^* value of CIE1976 color system. 10-60
Wherein the pearl pigment has a weight of 7%.
The thermoplastic resin coating layer comprising 0 to 100% by weight of dichroic interference mica titanium and having the glittering resin outermost layer formed thereon has a visible light transmittance of 25 to 85%;
(4). The transparent and colored or colorless heat which does not further impair the transparency on the glitter resin coating layer of the above (1) or the glitter resin outermost layer of the above (2) and (3). (5) that the outermost layer of the plastic resin is formed;
~ (7). A back surface resin coating layer made of a thermoplastic resin, which coats the back surface of the film material having the glittering resin coating layer of (1) to (3) on one surface, and a fiber knitted fabric for a base fabric, It has a lightness index L ^* value of the CIE1976 color system defined in JIS Z-8729-1980 of 10 to 60, and a porosity of the woven tissue of 15 to 40%, and the lightness index L ^{* of the} backside resin coating layer ^. Value is in the range of 10 to 60, and has a lightness index L ^* value different from that of the fiber knitted fabric for the base fabric, and the lightness index L of the fiber knitted fabric for the base fabric and the back surface resin coating layer ^* Value difference is 5-45, (8). A transparent and colored or colorless thermoplastic that does not further impair the transparency on the glitter resin coating layer of (5) or the glitter resin outermost layer of (6) or (7). When satisfying that the resin outermost layer is formed, the inventors have found that the knitting and weaving structure of the fiber cloth has sufficient glitter while being transparent, thereby completing the present invention. That is, the glittering composite film material of the present invention through which the knitting structure can be seen is (1). A base fabric made of a fiber knitted fabric, and covering at least one surface of the base fabric, and having a glittering resin coating layer containing 100 parts by weight of a thermoplastic resin and 0.5 to 10 parts by weight of a pearl pigment. The fiber knitted and woven fabric for a base fabric has a lightness index L ^* value of 10 in the CIE1976 color system specified in JIS Z-8729-1980.
Wherein the pearl pigment contains 70 to 100% by weight of the dichroic interference mica titanium, and the glittering resin coating layer has a visible light transmittance of 25 to 85% (JIS K). −6714-1988), and it is possible to see through the knitting structure of the fiber knitted woven fabric for the base fabric and to have glitter. The brilliant composite film material of the present invention which allows the woven structure to be seen through is (2). A base fabric made of a fiber knitted fabric, and covering at least one surface of the base fabric, and having a glittering resin coating layer containing 100 parts by weight of a thermoplastic resin and 0.5 to 10 parts by weight of a pearl pigment. On the surface of the glittering resin coating layer, a glittering resin outermost layer is further formed, and the glittering resin outermost layer is based on 100 parts by weight of the thermoplastic resin, and a pearl pigment contained in the glittering resin coating layer. Pearl pigments with different interference colors
10 parts by weight, and the fiber knitted and woven fabric for the base fabric is JI
CIE1 specified in SZ-8729-1980
Those having a lightness index L ^* value of 10 to 60 of 976 color system, the pearl pigment comprises 70 to 100 wt% of the dichroic interference titanated mica of its weight, the glitter resin outermost layer is formed 25-85% of the brilliant resin coating layer
Visible light transmittance (JIS K-6714-1988)
And the woven structure of the fiber knitted woven fabric for the base cloth can be seen through, and has brilliancy. The brilliant composite film material of the present invention through which the knitting structure can be seen is (3). A base fabric made of a fiber knitted woven fabric, and at least one surface of the base fabric, a transparent and colored, or having a colorless thermoplastic resin coating layer, on the surface of the thermoplastic resin coating layer, A glittering resin outermost layer containing 0.5 to 10 parts by weight of a pearl pigment with respect to 100 parts by weight of the thermoplastic resin is further formed, and the fiber knitted and woven fabric for the base cloth is JIS Z-8.
729-1980, having a CIE1976 color system lightness index L ^* value of 10 to 60, wherein the pearl pigment contains 70 to 100% by weight of its weight of dichroic interference mica titanium, The thermoplastic resin coating layer on which the glitter resin outermost layer is formed has a visible light transmittance (JIS K-6714-1988) of 25 to 85%, and the knitting structure of the fiber knitted fabric for the base cloth Can be seen through and has brilliancy. The brilliant composite film material of the present invention that allows the woven structure to be seen through is (4). The above (1)
A transparent, colored or colorless thermoplastic resin outermost layer is further formed on at least one outermost layer of the brilliant composite film material in which any one of (3) to (3) is visible. The glitter resin coating layer on which the glitter resin outermost layer is formed has a visible light transmittance of 25 to 85% (JIS K-6714-1988), and the fiber knitted woven fabric for the base fabric is The woven fabric can be seen through, and has brilliancy. The brilliant composite membrane material through which the knitting structure of the present invention can be seen through is a fiber knitted fabric for the base cloth,
It is preferable to be selected from a biaxial knitted fabric, a triaxial knitted fabric, and a four-axis knitted fabric having a knitted structure porosity of 0 to 40%. The brilliant composite film material of the present invention which allows the woven structure to be seen through is (5).
A base cloth made of a fiber knitted woven fabric, a glittering resin coating layer covering the surface of the base cloth, and containing 100 parts by weight of a thermoplastic resin and 0.5 to 10 parts by weight of a pearl pigment; And a back surface resin coating layer made of a thermoplastic resin.
CIE197 defined in Z-8729-1980
(6) a color index having a lightness index L ^* value of 10 to 60 and a porosity of a woven structure of 15 to 40%, and the pearl pigment contains 70 to 100% by weight of dichroic interference mica titanium. The glittering resin coating layer has a visible light transmittance (JIS K-6714-1988) of 25 to 85%, is capable of seeing through a knitted structure having a lightness index L ^* value, and has a glittering property. The lightness index L ^* value of the back surface resin coating layer is in the range of 10 to 60, and has a lightness index L ^* value different from the fiber knitted woven fabric for the base cloth, Lightness index L between the knitted fabric and the backside resin coating layer
^* Value difference is 5-45. The brilliant composite film material of the present invention which allows the woven structure to be seen through is (6). A base fabric made of a fiber woven fabric, and covering the surface of the base fabric, and
100 parts by weight of thermoplastic resin, pearl pigment 0.5 to 10
A glitter resin coating layer containing a weight part and a back resin coating layer covering the back surface of the base fabric and made of a thermoplastic resin, and further having a glitter surface on the surface of the glitter resin coating layer. A resin outermost layer is formed, and the glittering resin outermost layer contains 0.5 to 1 pearl pigment having a different interference color from the pearl pigment contained in the glittering resin layer with respect to 100 parts by weight of the thermoplastic resin.
0 parts by weight, and the fiber knitted fabric for the base fabric is JIS
CIE197 defined in Z-8729-1980
(6) a color index having a lightness index L ^* value of 10 to 60 and a porosity of a woven structure of 15 to 40%, and the pearl pigment contains 70 to 100% by weight of dichroic interference mica titanium. And wherein the glittering resin coating layer on which the glittering resin outermost layer is formed has a visible light transmittance of 25 to 85% (JI
Have S K-6714-1988), a openably knitting weave of lightness index L ^* value, and has a bright, lightness index L ^* value of the back resin coating layer, 10 6
0, and has a lightness index L ^* value different from the fiber knitted woven fabric for the base cloth, the lightness index L ^* value difference between the fiber knitted woven fabric for the base cloth and the back surface resin coating layer, 5-45
It is something that is. The brilliant composite film material of the present invention through which the knitting structure can be seen is (7). A base fabric made of a fiber knitted woven fabric, and a transparent and colored or colorless thermoplastic resin coating layer covering the surface of the base fabric, and covering the back surface of the base fabric, and A pearl pigment on the surface of the thermoplastic resin coating layer with respect to 100 parts by weight of the thermoplastic resin.
A glitter resin outermost layer containing 0 parts by weight is formed, and the fiber woven fabric for a base fabric is a lightness index L ^* value of a CIE1976 color system specified in JIS Z-8729-1980.
0 to 60, and a woven tissue porosity of 15 to 40%, wherein the pearl pigment has a weight of 70 to 100%.
% Of the dichroic interference mica titanium, and the thermoplastic resin coating layer on which the glittering resin outermost layer is formed is 25 to 8%.
5% visible light transmittance (JIS K-6714-198)
8), which can see through the knitted structure having a lightness index L ^* value, and has brilliancy, and the lightness index L ^* value of the back surface resin coating layer is in the range of 10 to 60. There, and has the lightness index L ^* value different from the base fabric for textile knitted woven fabric, the lightness index L ^* value difference based on the fabric for textile knitted woven fabric with the back resin coating layer, is from 5 to 45 Things. The brilliant composite film material of the present invention that allows the woven structure to be seen through is (8).
A base fabric made of a fiber knitted woven fabric; and 100 parts by weight of a thermoplastic resin, which covers the surface of the base fabric, and contains a pearl pigment 0.1 part by weight.
A glittering resin coating layer containing 5 to 10 parts by weight, and a backside resin coating layer made of a thermoplastic resin, which covers the back surface of the base cloth, and a surface of the glittering resin coating layer. Further, a transparent and colored or colorless thermoplastic resin outermost layer is formed thereon, and the fiber woven fabric for the base fabric is a CIE1976 color system defined in JIS Z-8729-1980. Lightness index L ^* value of 10 to 60,
And a woven tissue porosity of 15 to 40%,
The pearl pigment contains 70 to 100% by weight of the weight of the dichroic interference mica titanium, and the glittering resin layer on which the thermoplastic resin outermost layer is formed has a visible light transmittance of 25 to 85% (JISK). -6714-1988) have, an openably knitting weave of lightness index L ^* value, and has a bright, lightness index L ^* value of the back resin coating layer is 10 to 60 of It is within the range, and has a lightness index L ^* value different from the fiber knitted fabric for the base fabric, and the lightness index L ^* value difference between the fiber knitted fabric for the base fabric and the backside resin coating layer is 5 to 5. 45. In the glittering composite membrane material of the present invention, the fiber woven fabric for a base fabric is preferably a biaxial woven fabric, a triaxial woven fabric, or a four-axis woven fabric, wherein the fiber woven fabric for a base fabric has a porosity of 15 to 40%. It is preferable to be selected from The brilliant composite film material through which the knitting structure of the present invention can be seen,
The fiber knitted and woven fabric for base cloth is JIS Z-872-1.
A mixed knitted woven fabric of two or more types of fiber yarns different from each other in a lightness index L ^* value of the CIE1976 color system specified in 980, wherein each of the two or more types of fiber yarns has a lightness index L ^* value Is preferably 10 to 60. In the glittering composite film material of the present invention, the fiber woven fabric for the base fabric has a lightness index L ^* value of 10 to 60 in the CIE1976 color system specified in JIS Z-8729-1980. And a lightness index L ^* value of at least one fiber yarn having a value of 61 to 98 is preferably a mixed knitted woven fabric. In the glittering composite film material of the present invention, the fiber fabric for the base fabric is selected from carbon fiber multifilament yarn, aramid fiber multifilament yarn, and polyester multifilament fiber yarn. Preferably, it contains more than one species. The brilliant composite film material through which the knitting structure of the present invention can be seen,
It is preferable that the fiber knitted and woven fabric for a base fabric is composed of a multifilament yarn, and the yarn is colored with a pigment or a dye before or after spinning. In the glittering composite film material of the present invention, the textile fabric for the base fabric is made of a multifilament yarn, and the yarn contains 70 to 100% by weight of dichroic interference mica titanium. The surface is preferably coated with a paint containing a pearl pigment. The brilliant composite film material of which the weaving structure can be seen through the brilliant composite film material according to the present invention, wherein the formation of the brilliant resin outermost layer is performed by coating and drying a thermoplastic resin solution containing a pearl pigment, or includes a pearl pigment. It is preferably formed by laminating thermoplastic resin films. The brilliant composite film material of which the weaving structure can be seen through the brilliant composite film material according to the present invention, wherein the formation of the brilliant resin coating layer is performed by coating and drying a thermoplastic resin solution containing a pearl pigment, or contains a pearl pigment. It is preferably formed by laminating thermoplastic resin films. In the glittering composite film material of the present invention, the woven structure can be seen through, and the pearl pigment includes 70 to 99% by weight of dichroic interference mica titanium and 1 part of silver white mica titanium and / or chromatic mica iron oxide. -30% by weight. It is preferable that the glitter composite film material of the present invention in which the knitting structure can be seen through is formed with irregularities on the glitter resin coating layer, the glitter resin outermost layer, and the thermoplastic resin outer layer. The brilliant composite membrane material through which the knitting structure of the present invention can be seen through is a fiber woven fabric for the base cloth and the brilliant resin coating layer,
The color difference ΔE ^* ab (JIS Z-8729-1980) between the outermost layer of the glittering resin and the outermost layer of the thermoplastic resin is preferably 6.0 or more.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The glittering composite film material of the present invention, which allows a knitting structure to be seen through, is described in (1). A base fabric made of a fiber woven fabric,
And a glitter resin coating layer covering at least one surface of the base fabric and containing 100 parts by weight of a thermoplastic resin and 0.5 to 10 parts by weight of a pearl pigment, wherein the fiber knitted fabric for the base fabric is provided. Is a lightness index L ^* value of 10 to 6 of the CIE1976 color system specified in JIS Z-8729-1980.
0, wherein the pearl pigment contains 70 to 100% by weight of the dichroic interference mica titanium, and the brilliant resin coating layer has a visible light transmittance of 25 to 85% (JIS K- 6714-1988), or (2). A base fabric made of a fiber woven fabric,
And covering at least one surface of the base cloth, and having a glittering resin coating layer containing 100 parts by weight of a thermoplastic resin and 0.5 to 10 parts by weight of a pearl pigment, wherein the glittering resin coating layer has On the surface, a glitter resin outermost layer is further formed,
The glitter resin outermost layer contains 0.5 to 10 parts by weight of a pearl pigment having a different interference color from the pearl pigment contained in the glitter resin coating layer, based on 100 parts by weight of the thermoplastic resin,
The fiber knitted and woven fabric for a base cloth has a lightness index L ^* value of 10 to 60 in the CIE1976 color system, and the pearl pigment contains 70 to 100% by weight of the weight of the dichroic interference mica titanium. (3) the glitter resin coating layer on which the glitter resin outermost layer is formed has a visible light transmittance of 25 to 85%; A base fabric made of a fiber knitted fabric, and on at least one surface of the base fabric, a transparent and colored, or having a colorless thermoplastic resin coating layer, on the surface of the thermoplastic resin coating layer, Pearl pigment 0.5 to 100 parts by weight of thermoplastic resin
A glitter resin outermost layer containing 10 parts by weight is further formed,
The fiber knitted and woven fabric for a base cloth has a lightness index L ^* value of 10 to 60 in the CIE1976 color system, and the pearl pigment contains 70 to 100% by weight of the weight of the dichroic interference mica titanium. The thermoplastic resin coating layer on which the glitter resin outermost layer is formed has a visible light transmittance of 25 to 85%. (4). The transparent and colored or colorless heat which does not impair the transparency is further provided on the glitter resin coating layer of (1) or the glitter resin outermost layer of (2) or (3). A plastic resin outermost layer is formed, or (5) to (7). (1)-
(3) a backside resin coating layer made of a thermoplastic resin, which covers the back surface of the film material having a glittering resin coating layer on one side, and the fiber knitted fabric for the base fabric is JIS Z-8729.
The lightness index L ^* value of the CIE 1976 color system specified in -1980 is 10 to 60, and the porosity of the woven tissue is 15 to 4.
0%, the lightness index L ^* value of the back surface resin coating layer is in the range of 10 to 60, and has a lightness index L ^* value different from the fiber knitted woven fabric for the base cloth, (8) the difference in lightness index L ^* between the fiber knitted woven fabric for the base fabric and the backside resin coating layer is 5 to 45;
(5) the glittering resin coating layer or (6),
(7) A transparent, colored or colorless thermoplastic resin outermost layer which does not impair the transparency is further formed on the glittering resin outermost layer.

Here, the CIE1976 color system (JIS standard)
Z-8729)^* The value is 19
In 1976, the International Commission on Illumination (CIE) recommended "L^* a^* 
b^*L specified in the “color system and color difference formula”^* 116 (Y
/ Y₀ )^1/3 -16, a^* = 500 [(X / X₀ )^1/3 
− (Y / Y₀ )^1/3 ], B^* = 200 [(Y / Y₀ )
^1/3 − (Z / Z₀ )^1/3 ]. (Where X
₀ , Y₀ , Z₀ Is the tristimulus value X of the standard light used for illumination,
Y and Z are tristimulus values of the fiber fabric) CIE 1976 Table
The color system is the Adams-Nickerson color space (V_x ,
V_y , V_z Color space) in a simplified uniform color space
is there. The color difference is ΔE^* ab = [(ΔL^* ) ^Two + (Δa
^* ) + (Δb^* )]^1/2 It is represented by

[0011] The fiber knitted woven fabric which can be used for the glittering composite membrane material of the present invention which can be seen through the knitting structure includes fiber yarns constituting the fiber woven fabric, synthetic fibers, natural fibers, semi-synthetic fibers, regenerated fibers, and the like. Fiber knitted and woven fabrics selected from inorganic fibers and mixed fibers using two or more of these are woven and knitted. Preferably, these fiber yarns are colored by a pigment and a dye before spinning, or are colored after spinning. Further, a fiber woven fabric may be post-colored with a pigment and a dye.

[0012] The CIE1976 table of these fiber knitted and woven fabrics
Lightness index L based on color system (JIS standard Z-8729)^* value
Is in the range of 10 to 60, particularly preferably in the range of 15 to 45.
That is, the brilliant coloring effect of the brilliant composite film material of the present invention is
Higher is preferable. Lightness index L^* If the value exceeds 60,
It is not possible to obtain a brilliant coloring effect. Also brightness index
L^* The smaller the value, the brighter the coloring of the glittering composite film material of the present invention.
Properties are favorable, but L^* Value index less than 10
It is difficult to obtain fiber knitted and woven fabrics and fiber yarns
It is. In addition, the brightness index of the bright composite film material of the present invention is
L^* If the value is in the range of 10 to 60, the lightness index L^* Value of
Two or more different types of fiber yarns can be used. brightness
Exponent L^* Using two or more types of fiber yarns with different values
Therefore, the brilliant coloring effect of the brilliant composite film material of the present invention is partially reduced.
This is preferable because a slightly different visual effect can be obtained. Also lightness
Exponent L^* Fiber yarn whose value is in the range of 10 to 60, and lightness index
L ^* The value is in combination with a fiber yarn in the range of 61 to 98.
Is also good. Lightness index L^* Fiber yarn having a value in the range of 61 to 98
Brilliant coloring effect of the brilliant composite film material of the present invention
The result is a clear visual effect that can be
Good. Further, the fibers used in the glittering composite film material of the present invention
Weaving woven fabric has a lightness index L^* Value in the range of 10-60
Fiber knitted and woven fabric using fiber yarns and dichroism
Surface coating treatment with pearl pigment resin solution containing titanium interference mica
Knitted fiber knitting as one of the constituent types of woven fabric
It may be a woven fabric, and the lightness index L^* Value is 10-6
A fiber containing a fiber yarn in the range of 0 as one or more of the constituent species
A knitted fabric is made of a pearl pigment tree containing dichroic interference mica titanium.
It may be one that has been surface-coated with a fat solution. At this time
Heat is available for dichroic interference mica titanium used in resin solution
Interference with dichroic interference mica titanium compounded in plastic resin layer
Different colors are preferable for visual effect.

Among the fiber yarns that can be used in the glittering composite membrane material of the present invention, the synthetic fibers include polypropylene fiber, polyethylene fiber, vinylon fiber, and the like.
Acrylic fiber, polyurethane fiber, polyester fiber (polyethylene terephthalate, polybutylene terephthalate, polynaphthylene terephthalate), aromatic polyester fiber, nylon fiber (nylon-6, nylon-6,6), aramid fiber (poly-p-phenylene terephthalate) Amide (PPTA), poly-p-benzamide (PBA), p-phenylene-3,4-oxydiphenylene terephthalamide copolymer), polyether ether ketone (PEEK) fiber, polyphenylene sulfide fiber, polybenzthiazole (PBT) Fiber, polybenzoxazole (PBO) fiber, polybenzimidazole (PBI) fiber, and the like. Natural fibers include silk, cotton, wool and the like, semi-synthetic fibers include acetate fibers, and regenerated fibers include viscose rayon fibers and cupra fibers. Examples of the inorganic fibers include carbon fibers (PAN-based and pitch-based), glass fibers, and ceramic fibers (silica fiber, alumina fiber, potassium titanate fiber, titania fiber, silica-titania fiber, boron nitride fiber, boron carbide fiber, zirconia fiber). Fiber, silicon nitride fiber, silicon carbide fiber, silazane-silicon nitride fiber,
Silicon carbonitride fiber, alumina-boria-silica fiber)
And the like. The fiber fabric of the glittering film material of the present invention may use two or more kinds selected from these fibers, and may further use a mixed fiber composed of these two or more kinds of fibers. It is preferable that the fiber fabric of the glittering composite film material of the present invention is colored so that the lightness index L ^* value is in the range of 10 to 60. It is particularly preferred that the fiber fabric of the glittering film material of the present invention is a carbon fiber, an aramid fiber, and a colored polyester fiber.

It is preferable that these fiber yarns are multifilament yarns in the glittering composite film material of the present invention because the effect of expressing beautiful hairline gloss of the knitting structure is enhanced. These fibers have a filament diameter of 1-10μ
Single yarn obtained by twisting the strand obtained by converging 50 to 500 strands at 0 to 5 times / inch, or twisting two or three strands at 1 to 5 times / inch Multifilament fiber yarns such as twisted yarns are preferred. In particular, in the glittering film material of the present invention, the twist applied to the multifilament fiber yarn is preferably 0 to 2 times / inch, and optimally 0 times (no twist). This is preferable because the effect of expressing hairline gloss is enhanced. Further, the cross-sectional shape of the multifilament fiber yarn may be any of a circle, a square, an ellipse, a flat shape, and the like, but is preferably a flat shape. In the brilliant film material of the present invention, the use of flat multifilament fiber yarns is preferable because the effect of expressing a beautiful hairline luster of the knitted fabric seen through is further enhanced. In the present invention, it is also possible to use spun short fiber yarns, split fiber yarns, tape yarns, monofilament yarns, etc., but it is not possible to obtain a sufficient hairline gloss effect.

A woven or knitted fabric is preferable as the fiber knitted or woven fabric which can be used for the glittering composite membrane material of the present invention in which the knitted structure can be seen through. As the woven fabric, a plain woven fabric (having a minimum constitutional unit using at least two warp and weft yarns) and a twill woven fabric (having a minimum constitutional unit using at least three warp and weft yarns: 3 oblique, 4 woven Slanted, 5 slanted, 6 slanted, 8 slanted, etc., and satin woven fabrics (both warp and weft have a minimum unit of 5 units each: 2 jumps, 3 jumps, 4 jumps,
Regular jumps such as five jumps) can be preferably used. In addition, changing plain fabric, changing twill fabric, changing satin fabric obtained by enlargement method, exchange method, arrangement method, arrangement method, wefting method, thread cutting method, etc., as well as honeycomb fabric, nashiji fabric, tear oblique fabric , Day and night satin fabrics, woven fabrics (saori fabrics, gauze fabrics),
Sewing fabric, double fabric and the like can be mentioned.

The fiber knitted and woven fabric that can be used in the glittering composite membrane material of the present invention may have a woven structure in which the types of fibers used for the warp and the weft are different. For example, examples of such usage include a woven fabric using an aramid fiber yarn as a warp, a carbon fiber yarn as a weft, a woven fabric using a carbon fiber yarn as a warp, and a polyester fiber yarn as a weft. Further, any two or more of the above-described fiber yarns may be used in combination with the warp and the weft, and the respective fiber yarns may be alternately arranged at a constant driving interval. Are carbon fiber yarn (C) and aramid fiber yarn (Ar)
And the woven structure is {-C-Ar-}, ｛-CC
-Ar-｝, ｛-CCCC-Ar-｝ or the like as a repeating unit. Further, as such a usage, a knitted and woven fabric structure is formed by using a carbon fiber yarn (C) and a polyester fiber yarn (PET) and a ｛-C-PET.
-｝, ｛-CC-PET-｝, ｛-CCCC-PE
A knitted fabric structure or the like having T- と す る or the like as a repeating unit may be used. The polyester fiber yarn and the aramid fiber yarn used at this time may be left uncolored,
Further, any of those colored in the range of the lightness index L ^* value of 10 to 60 and those colored in the range of the lightness index L ^* value of 61 to 98 may be used. Further, the carbon fiber yarn may be surface-coated with a pearl pigment containing dichroic interference mica titanium.

As the knitted fabric, warp knitted fabric (connecting loops in the warp direction to form a fabric) includes denby knit, cord knit, atlas knit, and combination of denby knit and cord knit (half knit, reverse half). Other Russell drop plate structures, such as knitted fabric, French pile knitted fabric, velvet knitted fabric, combination of chain knitted fabric and satin knitted fabric (shark skin knitted, tusser knitted fabric, Delaware knitted fabric), combination of cord knitted fabric and cord knitted fabric (satin pile knitted fabric) A knit, an elastic knit, a weft insertion knit, a cut presser knit, and the like can be given. As a weft knit (connecting loops in the weft direction to form a cloth), a flat knit (table knit),
Rubber knitting (rib knitting), pearl knitting (garter knitting),
Knitted fabrics that use the tack effect on flat knitted fabrics (Namikanoko knitted fabric, floating fawned knitted fabric, Omotokonoko knitted fabric, Sonokonoko knitted fabric, herringbone knitted fabric), knitted fabrics that apply the tack action to rubber knitted fabric (one-sided knitting, double-sided knitting, milling turtle) Knitted fabrics, knitted fabrics using the tuck action (royal interlocked knitted fabrics, double-sided knitted fabrics, tuckle knitted fabrics), knitted fabrics that apply the welt effect to rubber knitted fabrics (Milan rib knit, single-bag knitted fabrics, blister knitted fabrics) , Beehive knitting), double-sided knitting with a welt effect (mock Milan rib knitting, mock rody knitting, well ripple knitting), lace knitting (tricot race knitting, raschel lace knitting, jacquard raschel lace knitting, torsion lace knitting, river lace) Knitting, plain net lace knitting, chemical lace knitting ), Other Eight lock knitting, eyelet knitting, pile knitted fabric, double face knitted fabric, such as intarsia knitting, and the like. These fabrics and knits can be woven and knitted using a conventional loom.

The above synthetic fiber multifilament yarn is
Thermoplastic resin such as polypropylene resin, polyethylene resin, vinylon resin, acrylic resin, polyurethane resin, polyester resin, aromatic polyester resin, nylon resin, etc. is heated to a temperature higher than the melting temperature (melting point) to flow viscous melt. Liquefied, and this is given a specific caliber (0.2 to
A known melt spinning method in which a long fiber spun raw yarn is extruded into an inert cooling medium such as air, nitrogen, or water through a spinneret having a large number of pores (approximately 0.6 mmφ), and rapidly cooled and solidified to obtain a long fiber spun yarn. And what was manufactured using equipment can be used.
In addition, the synthetic resin multifilament yarn is formed from a solution liquid crystal such as an aramid resin, a polybenzthiazole (PBT) resin, a polybenzoxazole (PBO) resin, or a polybenzimidazole (PBI) resin by a known wet-dry method. Can be used. It is preferable to color the multifilament yarn by blending an organic pigment, an inorganic pigment, a dye, etc., with the thermoplastic resin of the raw yarn material during production, and the lightness index of the multifilament yarn and the fiber knitted and woven fabric is preferable. L
^{* The} value is preferably in the range of 10-60. However, when these synthetic fiber multifilament yarns are mixed with other fiber yarns having a lightness index L ^* value of 10 to 60, those having a lightness index L ^* value of 61 to 98,
Alternatively, it may be uncolored.

As the organic pigment for coloring the multifilament yarn, azo pigments, more specifically, as insoluble monoazo pigments, β-naphthol, naphthol AS, organic acetoacetate arylamide pigments, and insoluble disazo pigments Phthalocyanine pigments such as acetoacetate arylamide-based, pyrazolone-based organic pigments, azo lake pigments such as β-naphthol-based, β-oxynaphthoic acid-based organic pigments, condensed azo pigments, and metal complex salt azo pigments. Are dyed lake pigments such as copper phthalocyanine, halogenated copper phthalocyanine, metal-free phthalocyanine, and copper phthalocyanine lake; more specifically, acid-dye lake pigments, basic dye lake pigments; and condensed polycyclic pigments; more specifically, anthraquinone-based pigments. Pigments, thioindigo pigments, perinone pigments, Rylene pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, isoindoline pigments, and other organic pigments such as nitroso pigments, alizarin lake pigments, metal complex azomethine pigments, aniline pigments, and more One or more of these organic pigments can be used. These organic pigments can be used in combination with inorganic pigments. As a method of coloring the multifilament yarn and the fiber cloth, a method of coloring after knitting and weaving a fiber knitted woven cloth may be used in addition to the above-described primary yarn primary color method. As one of the methods, there is a method of coloring and coating a fiber woven fabric using a synthetic resin binder containing the organic pigment, for example, a dipping method, a coating method, a film laminating method, and the like. There is no particular limitation on the synthetic resin binder, but polyvinyl chloride resin, polyurethane resin, acrylic resin, vinyl acetate resin, polyvinyl alcohol resin, ethylene-vinyl acetate copolymer resin, polystyrene resin, saturated polyester resin , Polyamide resins and modified resins thereof can be used. These synthetic resins can be selected from those solubilized in an organic solvent or those emulsified in an aqueous solution depending on the production method and texture design. If necessary, a crosslinking agent such as an isocyanate compound, an oxazoline compound, a carbodiimide compound, an aziridine compound, and an epoxy compound, and a curing agent can be used. Further, a thermosetting resin such as a phenol resin, a melamine resin, a urea resin, an unsaturated polyester resin, an epoxy resin, a thermosetting polyurethane resin, and an allyl phthalate resin can be blended and used. .

As another method, dyeing with a dye is preferred. As dyes that can be used for dyeing fiber fabrics, conventionally known dyes such as natural dyes and synthetic dyes, for example, disperse dyes such as azo dyes and anthraquinone dyes include polyester fibers, acetate fibers, nylon fibers,
It can be used for dyeing hydrophobic fibers such as vinylon fiber and polypropylene fiber.For example, a cationic dye such as triphenylmethane dye, azo dye, anthraquinone dye or polymethine dye can be used for dyeing acrylic fiber. For example, an amino group, or a basic dye such as a triphenylmethane dye having a basic property such as a substituted amino group, an azo dye, or a polymethine dye can be used for dyeing nylon fibers, polyamide fibers, and silk. For example, azo dyes, anthraquinone dyes, acid dyes such as triphenylmethane dyes can be used for dyeing wool, silk, nylon fibers, for example, hydroxyl group,
Nylon fiber, silk,
It can be used for dyeing cotton and the like.For example, a direct dye such as a bisazo dye having a sulfonic acid group and a trisazo dye can be used for dyeing cotton, viscose rayon fiber, and polynosic fiber. Vat dyes such as anthraquinone dyes having a structure and indigoid dyes can be used for dyeing cotton and rayon fibers.For example, a coupling reaction is performed on a fiber with a developer of a diazo component to form an insoluble azo dye. Azoic dyes can be used to dye cotton, for example, other,
Nitroso, nitro, stilbene, quinoline, thiazole, indamine, indophenol, azine, oxazine, thiazine, aminoketone, oxyketone, and phthalocyanine dyes can be used.
Known dyeing methods such as a dyeing pad method, a batch method, a continuous dyeing method, and a printing method can be used as the dyeing method.

As the carbon fiber multifilament yarn, an acrylic fiber multifilament yarn obtained by melt-spinning polyacrylonitrile (PAN) is used as a precursor and heated at 200 to 300 ° C. in air to perform a flameproofing treatment. PAN-based carbon fibers produced by heating at 1000 to 1500 ° C. in an inert gas to accelerate the carbonization reaction can be used. As another production method, a fiber obtained by melt-spinning a precursor pitch made from an aromatic hydrocarbon such as petroleum tar or coal pitch is made infusible by heating at 150 to 400 ° C. in an oxidizing atmosphere. Then, pitch-based carbon fibers produced by a method of promoting carbonization by heating at 800 to 1500 ° C. in an inert gas can be used. These carbon fibers may be graphitized by heating at 2000 to 3000 ° C. in an inert gas. If necessary, those subjected to a surface oxidation treatment, a surface activation treatment, and a surface graft treatment can also be used.

In particular, in a fiber woven fabric or a carbon fiber multifilament yarn woven or woven from carbon fiber multifilament yarns, 70 to 99% by weight of dichroic interference mica titanium or dichroism interference mica titanium remains. As a component in an amount of 1 to less than 30% by weight, a resin coated with a resin containing a pearl pigment containing silver white mica titanium and / or chromatic mica iron oxide can be used. Examples of the resin solution include a resin solution in which a thermoplastic resin is solubilized or dispersed in an organic solvent, and a resin emulsion in which a thermoplastic resin is emulsified (polymerized) or suspended (polymerized) in water, and a dispersion. A resin-containing solution, and a thermoplastic resin solid content of 100% by weight in the resin solution.
0.5 to 10% by weight of dichroic interference mica titanium and uniformly dispersing them. At this time, it is preferable from the viewpoint of visual effect that the dichroic interference mica titanium compounded in the resin solution has a different interference color from the dichroic interference mica titanium compounded in the thermoplastic resin layer. Thermoplastic resins suitable for use after being dissolved in an organic solvent include soft polyvinyl chloride resins, polyurethane resins, ethylene-vinyl acetate copolymer resins, and ethylene- (meth) acrylic acid (ester) copolymers. Coalescing resin,
An acrylic copolymer resin, a styrene copolymer resin, a polyester copolymer resin, a polyamide copolymer resin and the like can be mentioned. Examples of thermoplastic resins that can be used in a water-dispersed state such as a resin emulsion and a dispersion include soft polyvinyl chloride resins, polyurethane resins, ethylene-vinyl acetate copolymer resins, and ethylene-vinyl acetate resins.
Examples thereof include (meth) acrylic acid (ester) copolymer ionomer resin, acrylic copolymer resin, styrene copolymer resin, polyester copolymer resin, and polyamide copolymer resin. The resin solution can be coated by, for example, a gravure method or a dipping method. The surface of the fiber woven fabric coated with the resin solution containing the pearl pigment is further coated with dichroic interference mica titanium in an amount of 0.5 to 100% by weight of the thermoplastic resin solid content.
A brilliant resin coating layer containing 10 to 10% by weight can be formed, and a thermoplastic resin layer containing no pearl pigment can also be formed. Further, the surface of the thermoplastic resin layer containing no pearl pigment may be surface-treated with a resin solution containing pearl pigment. It is preferable from the viewpoint of visual effect that the interference colors of the dichroic interference mica titanium used at this time are different from each other.

Glass fiber multifilament yarn and ceramic fiber multifilament yarn (silica fiber,
Alumina fiber, potassium titanate fiber, titania fiber,
Known zirconia fibers, such as melt spinning, melt precipitation, precursor impregnation, melt spinning-infusibility, and dry spinning (slurry, sol-gel, solution, and precursor polymer methods). What was obtained by the spinning method can be used. For coloring these fibers, inorganic pigments can be preferably used. As inorganic pigments that can be used, black pigments such as carbon black, titanium black, acetylene black, and graphite can be preferably used, and as other inorganic pigments, zinc oxide, titanium oxide (rutile type, anatase type), antimony trioxide, Iron oxide, yellow iron oxide, ferrosyanide, lead oxide, chromium oxide, zirconium oxide,
Metal oxides such as cobalt oxide, cobalt phosphate, and manganese phosphate, and composite metal oxides thereof, such as calcium sulfide, strontium sulfide, zinc sulfide, zinc cadmium sulfide, cadmium sulfide, and metal sulfides such as mercury sulfide; and Barium sulfate, such as these composite metal sulfides,
Metal sulfates such as calcium sulfate, lead sulfate and basic lead sulfate, and composite metal sulfates thereof; metal carbonates such as barium carbonate, magnesium carbonate, and lead carbonate; and hydroxides of these composite metal carbonates Aluminum, metal hydroxides such as chromic acid hydrate, and composite metal hydroxides thereof, such as lead chromate, zinc chromate, barium chromate, and the like, and composite metal chromate salts thereof And other spinel type (XY ₂ O
₄ ) Structural oxide: * XY = Co-Al, Co-Al-C
r, Co-Mg-Sn, Co-Ni-Ti, Co-Zn
-Ni-Ti, Co-Zn-Cr-Ti, Zn-Cr-
Ti, Zn-Cr-Fe, Co-Zn-Cr-Fe, C
o-Ni-Cr-Fe-Si, Co-Mn-Cr-F
e, Cu-Mn-Cr, Mn-Fe, etc., rutile type [T
i (XY) O _2] structure oxide: XY = Pb-Sb, Ni
-Sb, Ni-W, Fe-Mo, Cr-Sb and the like. As a method of coloring these fibers, a method of coloring after knitting and weaving a fiber knitted or woven fabric may be used in addition to the above-described original yarn dipping method. As one of the methods, there is a method of coloring and coating a fiber woven fabric using a synthetic resin binder containing the organic pigment, for example, a dipping method, a coating method, a film laminating method, and the like.
There is no particular limitation on the synthetic resin binder, but polyvinyl chloride resin, polyurethane resin, acrylic resin, vinyl acetate resin, polyvinyl alcohol resin, ethylene-vinyl acetate copolymer resin, polystyrene resin, saturated polyester resin , Polyamide resins and modified resins thereof can be used. These synthetic resins can be selected from those solubilized in an organic solvent or those emulsified in an aqueous solution depending on the production method and texture design. If necessary, isocyanate compounds, oxazoline compounds, carbodiimide compounds,
Aziridine compounds, crosslinking agents such as epoxy compounds, and
A curing agent or the like can be used. Further, a thermosetting resin such as a phenol resin, a melamine resin, a urea resin, an unsaturated polyester resin, an epoxy resin, a thermosetting polyurethane resin, and an allyl phthalate resin can be blended and used. .

Further, the surface of the fibrous woven fabric which can be used for the glittering composite film material of the present invention which allows the woven structure to be seen through may be metal-deposited. As metal deposition, known resistance heating deposition, electron beam deposition, ion plating, sputtering, high-speed sputtering, chemical vapor deposition (CVD),
A plasma CVD method or the like can be used. Examples of the deposition material include Ag, Au, Cu, Al, Zn, Mg,
Examples include Sn, Ni, Co, Mo, W, and TiC.

The multifilament yarn used for the fiber fabric of the brilliant composite film material through which the knitting structure of the present invention can be seen is 100 (111 dtex) to 3000 (3333 d).
tex) denier, especially 200 (222 dtex) ~
A 2000 (2222 dtex) denier multifilament yarn can be used. 10 multifilament yarns
If it is less than 0 denier, the knitting structure of the fiber knitted and woven fabric becomes too fine and lacks a three-dimensional effect, so that the appearance of the glittering composite film material obtained becomes ordinary. Therefore, as the weaving structure becomes larger, the appearance becomes more unexpected and more designable.
If it exceeds 0 denier, the resulting brilliant composite film material becomes unnecessarily thick and heavy, which is not preferable. There is no particular limitation on the number of warp yarns and weft yarns of the fiber knitted and woven fabric.
In the case of a knitted and woven fabric obtained by driving 10 to 150 denier multifilament yarns into warp and weft yarns per inch, for example, a 750 (833 dtex) denier multifilament yarn is 16 per inch.
Plain knitted woven fabric obtained with a driving number of ~ 26, 1500
In the case of a (1665 dtex) denier multifilament yarn, a plain knitted fabric obtained by driving about 10 to 16 fibers per inch can be exemplified. The fiber knitted and woven fabric of the glittering composite membrane material of the present invention has a flat warp and weft of 1000 to 1000.
A biaxial flat knitted fabric obtained by using a 2000 denier multifilament fiber yarn,
The appearance is preferable because the effect of expressing the beautiful hairline gloss of the see-through knitted fabric becomes higher.

In addition, the fiber knitted woven fabric of the glittering composite membrane material of the present invention which allows the knitting structure to be seen through may be a triaxial knitted woven fabric or a 4-axis knitted woven fabric. Examples of the triaxial knitted fabric include a fabric composed of three yarns selected from the above-mentioned multifilament yarns and woven so that the intersection angle between the yarns is 60 °. As the triaxial knitted fabric, a woven fabric composed of a warp and two bias (oblique) yarns is preferred because the stability of the fabric structure in the processing direction is high. The four-axis knitted fabric is composed of four yarns selected from the multifilament yarns, and includes a warp and a weft which are orthogonal to each other, and further intersects the warp and the weft at an angle of 45 °. And a woven fabric containing the bias yarn. The number of warp yarns, weft yarns and bias yarns of the triaxial knitted fabric and the quadriaxial knitted fabric is not particularly limited. 0.5 to 30 woven fabrics, for example, a 500-denier multi-filament yarn, a triaxial knitted fabric or a 4-axial knitted fabric obtained at a number of 1 to 20 per inch per 1 inch, a 1000 denier mulch 0.5 per inch for filament yarn
Examples include a triaxial knitted fabric or a quadriaxial knitted fabric obtained with about 15 to about the number of driving.

The woven fabric porosity of the above-mentioned fibrous woven fabric used in the glittering composite film material of the present invention is 0 to 40%, preferably 0 to 20%, and particularly preferably 0 to 40%. It is preferably a 10% high density knitted fabric. If the porosity of the woven fabric exceeds 40%, not only the effect of bright color development is not sufficiently obtained, but also the dimensional stability in the longitudinal direction is poor, so it is used for applications such as sunshade tents, cover materials, interior materials and decorative sheets. It is not suitable for doing. The woven fabric porosity can be obtained as a value obtained by calculating the area of the fiber yarn occupying a unit area of the fiber woven fabric as a percentage and subtracting it from 100. It is convenient and preferable to determine the porosity of the woven tissue as a unit area of 10 cm in the warp direction × 10 cm in the weft direction.

The dichroic interference mica titanium which can be used in the glittering composite film material of the present invention, which can be seen through, has a particle size of 5
A pearl pigment in which titanium dioxide is coated at a coverage of 43 to 80% on the surface of mica scales of 100 μm. For example, if the coverage of titanium dioxide is 43%, a dichroic interference mica titanium having a reflection color of gold and a transmission color of violet is obtained. If the coverage is 47%, a reflection color of orange and a transmission color of green are obtained. When dichroic interference mica titanium is obtained and the coverage is 52%, dichroic interference mica titanium having a reflection color of blue and a transmission color of yellow is obtained, and the coverage is 57%.
%, A dichroic interference mica titanium having a green reflection color and a red transmission color is obtained. These dichroic interference mica titaniums may be used as a blend of two or more. Further, these dichroic interference mica titanium can be used in combination with pearl pigments such as silver white mica titanium and chromatic mica iron oxide, and in the case of this combination, two colors are used based on the total amount of pearl pigment used. It is preferable to contain 70 to 99% by weight of the ionic interference mica titanium. If the content of the dichroic interference mica titanium is less than 70% by weight, the resulting brilliant composite film material has insufficient colored brilliancy and transparency of the knitted structure, which is not preferable. Examples of the silver-white mica titanium include pearl pigments obtained by coating titanium dioxide on the surface of mica scales having a particle size of 5 to 100 μm at a coverage of 12 to 42%. The chromatic mica iron oxide is a gold chromatic color in which mica scales having a particle size of 5 to 100 μm are coated with titanium dioxide at a coverage of 12 to 50%, and further coated with iron oxide (II) at a coverage of 2 to 30%. Pearl pigments. Bronze chromatic pearl pigments in which iron oxide (II) is coated on the surface of mica scales having a particle size of 5 to 100 μm at a coverage of 20 to 60% are also exemplified. These dichroic interference mica titanium can be used by blending two or more kinds, and the dichroic interference used for the structural layer by forming the glitter resin coating layer of the glitter composite film into a multilayer structure. It is also preferable from the viewpoint of visual effect to use titanium mica as different ones.

These dichroic interference mica titanium or 70-99% by weight of dichroic interference mica titanium and the remaining 1-30
The amount of the pearl pigment containing silver white mica titanium and / or chromatic mica iron oxide as a component of less than weight% is 0.5 to 0.5 parts by weight per 100 parts by weight of the thermoplastic resin depending on the design thickness of the glittering resin coating layer. 10 parts by weight, preferably 1.0 to 5.
It is preferable to contain it in the range of 0% by weight. When the blending amount is less than 0.5% by weight, the resulting glittering composite film material is inferior in color-developed glittering properties. It is not preferable because it is insufficient. The visible light transmittance (JIS standard K) of the glittering resin coating layer containing dichroic interference mica titanium.
-6714) is preferably from 25 to 85%. If the visible light transmittance is less than 25%, the resulting brilliant composite film material has a beautiful hairline gloss, and the appearance of the glossiness is inadequate, resulting in an unfavorable appearance, which is undesirable.
If it exceeds 5%, the resulting glittering composite film material is inferior in the coloring glittering properties, which is not preferable. In the glitter composite film material of the present invention, the glitter resin coating layer may be transparently colored with an organic pigment as long as the visible light transmittance is in the range of 25 to 85%.
Further, the color difference Δ between the fiber knitted fabric and the obtained glittering composite film material
E ^* ab (JIS standard Z-8729) is preferably 6.0 or more. When the color difference ΔE ^* ab is less than 6.0,
The resulting glittering composite film material is inferior in the coloring glittering properties, so that the appearance becomes monotonous, which is not preferable. When the color difference ΔE ^* ab of the glitter composite film material of the present invention is 6.0 or more, and preferably 10 or more, it is preferable because more unexpected color development glitter can be obtained.

The thermoplastic resin which can be used for the glittering composite film material of the present invention which can be seen through the knitting structure, contains titanium dichroic interference mica and has a transparency satisfying the above light transmittance of 35 to 85%. There is no particular limitation as long as it is a resin which can be obtained, but soft polyvinyl chloride resin, polyethylene resin, polypropylene resin, ethylene-α-olefin copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene- ) Acrylic acid (ester) copolymer resin, polyolefin resin elastomer, acrylic resin elastomer, styrene resin elastomer, polyurethane resin elastomer, polyester resin elastomer, polyamide resin elastomer, polyvinylidene fluoride resin elastomer, etc. Can be Particularly preferably, a soft polyvinyl chloride resin containing 35 to 85 parts by weight of a plasticizer, a linear low-molecular resin obtained by ionic copolymerization of an ethylene monomer and an α-olefin having 3 to 18 carbon atoms in the presence of a metallocene catalyst. Ethylene-α-olefin copolymer resin which is a high-density polyethylene, ethylene-vinyl acetate copolymer resin obtained by radical copolymerization of an ethylene monomer with a vinyl acetate monomer having a concentration of 6 to 35% by weight, and an ethylene monomer having a concentration of 6 to 35 Ethylene- (meth) acrylic acid (ester) copolymer resin, ester-based polyurethane resin, caprolactam-based polyurethane resin, ether-based polyurethane-based resin obtained by radical copolymerization with a (%) concentration of (meth) acrylic acid (ester) monomer Use resin, carbonate-based polyurethane resin, etc. Can be

The glittering resin coating layer of the glittering composite film material of the present invention, which allows the woven structure to be seen through, can be used by blending an appropriate amount of an additive, if necessary. In particular, for the purpose of improving the durability of the glittering resin coating layer, an ultraviolet absorber, an antioxidant,
It is preferable to add 0.1 to 3.0 parts by weight of a light stabilizer or the like. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylic acid-based, and anilide-based ultraviolet absorbers, and examples of the antioxidant include hindered phenol-based, amine-based, and phosphite-based antioxidants. . Examples of the light stabilizer include hindered amine light stabilizers. In addition, metal soap, phosphate ester type, aliphatic amide type and montanic acid type lubricants are added in order to improve the processability during film forming.
It is preferable to add 1 to 2.0 parts by weight.

The method for producing the glittering resin coating layer of the glittering composite film material of the present invention capable of seeing through the knitting structure can be performed by a conventionally known molding method, for example, a T-die extrusion method, an inflation method, a calendering method or the like. can do.
The compound of the brilliant resin coating layer may be formed by a known method, for example, using a Banbury mixer, a kneader, a biaxial kneader, or the like, with 100 parts by weight of the thermoplastic resin, dichroic interference mica titanium, or dichroic interference mica. 0.5 to 10 parts by weight of a pearl pigment-containing composition containing silver-white mica titanium and / or chromatic mica iron oxide, with titanium being 70 to 99% by weight and the remaining component being less than 1 to 30% by weight, and others The compound can be obtained by a method in which the additive and the additive are collectively kneaded and kneaded to form a compound, and a method in which after melt-kneading, the mixture is granulated and pelletized with a single-screw extruder, a twin-screw extruder, or the like. The brilliant resin coating layer of the brilliant composite film material of the present invention is obtained by using the above-mentioned granulated pellets and a compound to form a T-
Although it can be manufactured by processing techniques such as die extrusion, inflation and calendering, the calendering method is particularly suitable for the production of films colored with pearl pigments, etc. Simple and suitable with low loss. The glitter resin coating layer of the glitter composite film material of the present invention is preferably subjected to a film forming process at a temperature in the range of 100 to 200 ° C. by a calender method.

The thickness of the film of the glittering resin coating layer to be calendered is 80 to 500 μm, especially 120 to 40 μm.
It is preferably 0 μm. If the thickness is less than this range, it is difficult to mold, and when laminating and laminating on a fiber cloth, the film breaks at the intersection of the fiber knitted and woven fabric, which not only impairs the appearance but also the glittering composite film material Deteriorate the durability of the Although the thickness of the glittering composite film material of the present invention is not limited, it is preferable to laminate and laminate with a fiber woven fabric using one or two films of a glittering resin coating layer having a thickness of 80 to 500 μm. In particular, it is preferable to use two or more films each having a thickness of 120 to 400 [mu] m and form a glitter resin coating layer on one or both surfaces of the fiber knitted or woven fabric. Further, two or more glittering resin coating layers using dichroic interference mica titanium having different interference colors may be provided, and the visible light transmittance (JIS K-67) of the glittering resin coating layer may be provided.
14) is not particularly limited as long as the thickness ratio of each film layer is within the range of 25 to 85%. When the glittering resin coating layers are formed on both surfaces of the fiber woven fabric, the interference color and the blending amount of the dichroic interference mica titanium in the surface layer and the back surface layer may be different from each other. If not necessary, the dichroic interference mica titanium in the back layer can be omitted. In particular, the lightness index L ^* value of the colored backside thermoplastic resin layer formed on the backside is 10 to 60, and the lightness index L ^* of the fiber knitted woven fabric varies within the range of 10 to 60 ^. Preferably it has a value. Further, it is particularly preferable that one or more films having a thickness of 120 to 400 [mu] m are used to form a glitter resin coating layer on one surface of a fiber woven fabric. Further, the glitter resin coating layer of the glitter composite film material of the present invention can be used by laminating a thermoplastic resin film containing a pearl pigment and a thermoplastic resin film containing no pearl pigment. The thermoplastic resin film containing no pearl pigment is obtained by the same manufacturing method as the thermoplastic resin film containing a pearl pigment, and has a thickness of 80 to 5 mm.
Those having a size of 00 μm, particularly 120 to 400 μm can be used. When laminating these films, the thermoplastic resin film layer containing a pearl pigment may be the outermost layer of the glittering resin, or the thermoplastic resin film layer containing no pearl pigment may be the outermost layer. In particular, in the case of the latter laminated type, the woven structure of the brilliant composite film material of the present invention is brilliant, rich in three-dimensional appearance, and visually preferable. The same kind of effect can be obtained similarly by the former type of lamination. Visible light transmittance (JI) of these glittering resin coating layers
As long as S standard K-6714) is within the range of 25 to 85%, there is no particular limitation on the thickness ratio of each film layer, and the film layer may be colored. Further, the thermoplastic resin film containing no pearl pigment may be non-colored and transparent, or may be transparently colored with an organic pigment or dye. This transparent coloring preferably has a hue different from that of the dichroic interference mica titanium used for another layer in terms of visual effect. As organic pigments that can be used for transparent coloring of thermoplastic resin films, azo pigments, more specifically, as insoluble monoazo pigments, β-naphthol, naphthol A
S-based, acetoacetate arylamide-based organic pigments, as insoluble disazo pigments, acetoacetate arylamide-based pigments,
As pyrazolone-based organic pigments and azo lake pigments, β
-Dyeing of phthalocyanine pigments such as naphthol-based, β-oxynaphthoic acid-based organic pigments, condensed azo pigments, metal complex salt azo pigments, and more specifically, copper phthalocyanine, halogenated copper phthalocyanine, metal-free phthalocyanine, copper phthalocyanine lake, Lake pigments, specifically, acid dye lake pigments, basic dye lake pigments, etc., condensed polycyclic pigments, specifically, anthraquinone pigments, thioindigo pigments, perinone pigments, perylene pigments, quinacridone pigments, dioxazine pigments Pigments, isoindolinone pigments, quinophthalone pigments, isoindoline pigments,
Other organic pigments include nitroso pigments, alizarin lake pigments, metal complex azomethine pigments, aniline pigments,
One or more of these organic pigments can be used. These organic pigments can be used in combination with a dye. As dyes, natural dyes,
Conventionally known dyes such as synthetic dyes, for example, azo dyes, anthraquinone dyes, triphenylmethane dyes, polymethine dyes, bisazo dyes, trisazo dyes, indigoid dyes, azoic dyes, and other nitroso and nitro dyes And stilbene, quinoline, thiazole, indamine, indophenol, azine, oxazine, thiazine, aminoketone, oxyketone, and phthalocyanine dyes.

Further, the glittering composite film material of the present invention, which allows the see-through of the knitting structure, has a lightness index L ^* value of 10 to 60, and has a porosity of 15 to 40% for a fiber knitted or woven fabric on one surface.
0.5 to 1 pearl pigment containing 70 to 100% by weight of dichroic interference mica titanium based on 100 parts by weight of thermoplastic resin
0 parts by weight of visible light transmittance (JIS standard K-67)
14) is a glitter resin coating layer having a brightness index L ^* of 25 to 85%, and a lightness index L ^* having a lightness index L ^* value of 10 to 60, which is different from the lightness index L ^* value of the fibrous woven fabric ^.
A backside thermoplastic resin layer having a value may be formed. The backside thermoplastic resin layer having a lightness index L ^* value of 10 to 60 formed on the backside of the fibrous woven fabric is preferably a mixture of the thermoplastic resin described above with an organic pigment and an inorganic pigment. This composite membrane material has a visible light transmittance of 25 to 8 containing dichroic interference mica titanium formed on the surface in a fibrous woven fabric having a woven tissue porosity of 15 to 40%.
The glittering resin coating layer of 5% and the backside thermoplastic resin layer having a lightness index L ^* value of 10 to 60 formed on the backside are partially bonded to each other. A lightness index L ^* value of this time the fibers knitted woven fabric, lightness of the back thermoplastic layer L ^*
Values are different from each other, and the lightness index L ^* value difference is 5 to 4
It is preferably 5. If the lightness index L ^* value difference is less than 5, the color appearance of the obtained composite film material becomes monotonous, which is not preferable, and if the lightness index L ^* value difference exceeds 45, the voids of the fiber knitted woven fabric of the obtained composite film material become It is not preferable because the color brilliancy is poor. Lightness index L ^* Value difference is 5 to 45
In the composite film material within the range, the surface glittering resin coating layer formed on the fiber knitted woven fabric and the back surface thermoplastic resin layer formed in the void portion of the fiber knitted woven fabric exhibit different coloring glittering properties. Therefore, the appearance of the composite membrane material can be unexpectedly obtained, which is preferable.

As the organic pigment for coloring the rear thermoplastic resin layer, azo pigments, more specifically, as insoluble monoazo pigments, β-naphthol, naphthol AS, acetoacetic arylamide organic pigments, insoluble disazo pigments Phthalocyanine pigments such as acetoacetate arylamide-based pigments, pyrazolone-based organic pigments, and azo lake pigments such as β-naphthol-based, β-oxynaphthoic acid-based organic pigments, condensed azo pigments, and metal complex salt azo pigments; Specifically, dyeing lake pigments such as copper phthalocyanine, halogenated copper phthalocyanine, metal-free phthalocyanine, and copper phthalocyanine lake; more specifically, condensed polycyclic pigments such as acid dye lake pigment and basic dye lake pigment; and more specifically, anthraquinone Pigments, thioindigo pigments, perinone pigments, Emissions-based pigments, quinacridone pigments,
Dioxazine pigments, isoindolinone pigments, quinophthalone pigments, isoindoline pigments, and other organic pigments such as nitroso pigments, alizarin lake pigments, metal complex azomethine pigments, aniline pigments, and one of these organic pigments Alternatively, two or more kinds can be used. These organic pigments can be used in combination with inorganic pigments.

As the inorganic pigment for coloring the backside thermoplastic resin layer, black pigments such as carbon black, titanium black, acetylene black, and graphite can be preferably used. Other inorganic pigments include zinc oxide, titanium oxide (rutile type). , Anatase type), metal oxides such as antimony trioxide, iron oxide, yellow iron oxide, ferrocyanide, lead oxide, chromium oxide, zirconium oxide, cobalt oxide, cobalt phosphate, manganese phosphate, and composite metals thereof Oxides, such as calcium sulfide, strontium sulfide, zinc sulfide, zinc cadmium sulfide, cadmium sulfide,
Metal sulfides such as mercury sulfide, and their composite metal sulfides, such as barium sulfate, calcium sulfate, lead sulfate, and basic lead sulfate; and their composite metal sulfates, such as barium carbonate and magnesium carbonate Metal hydroxides such as lead carbonate, and composite metal carbonates thereof, such as aluminum hydroxide, metal hydroxides such as chromic acid hydrate, and composite metal hydroxides thereof, such as lead chromate and chromate Zinc, metal chromate salts such as barium chromate, and their composite metal chromate salts, etc.
Spinel type (XY ₂ O ₄ ) structure oxide: * XY = Co-
Al, Co-Al-Cr, Co-Mg-Sn, Co-N
i-Ti, Co-Zn-Ni-Ti, Co-Zn-Cr
-Ti, Zn-Cr-Ti, Zn-Cr-Fe, Co-
Zn-Cr-Fe, Co-Ni-Cr-Fe-Si, C
o-Mn-Cr-Fe, Cu-Mn-Cr, Mn-Fe
Such as rutile [Ti (XY) O _2] structure oxide: XY
= Pb-Sb, Ni-Sb, Ni-W, Fe-Mo, C
r-Sb and the like.

The above-described fiber woven fabric and glittering resin coating film, and a transparent, colored or colorless thermoplastic resin coating film, or a colorless transparent or transparent colored thermoplastic resin outermost layer As a method of lamination and lamination with a film, an adhesive layer may be provided between each of these films and the fiber knitted or woven fabric, or lamination without an adhesive may be performed. The laminating method used for the glittering composite film material of the present invention may be a calendar topping method or a T-die extrusion laminating method in which a laminating process is performed on each of these films simultaneously with a fiber knitted fabric, or a calendering method or a T-die extrusion method. After each of these films is formed by a single process using a laminator having an infrared heater,
A method of laminating a sheet of glittering resin coating film and a thermoplastic resin layer film at a time by thermocompression bonding and laminating with a coarse fiber knitted woven fabric. Is a glittering resin coating layer film molded and processed by the calendar method, and a transparent, colored, or colorless thermoplastic resin coating film, or a transparent, colored, or colorless A production method by thermocompression bonding between the thermoplastic resin outermost layer film and the fiber knitted or woven fabric is preferable because it is efficient and economical. At this time, since the two glittering resin coating layer films on the front and back and the thermoplastic resin layer film are bridged by heat fusion via the void portion of the fiber knitted and woven fabric, application of a special adhesive and extra This is preferable because good adhesion and durability can be obtained without requiring a complicated process. In particular, in the case of laminating and laminating a glittering resin coating layer film on only one side using a fibrous knitted woven fabric having a woven fabric void portion of less than 10%, it is preferable that the fibrous woven fabric is subjected to an adhesive treatment. As the adhesive, an adhesive composed of the same type or the same type of resin as that of the glittering resin coating film is preferable. For example, when laminating and laminating a polyurethane resin film on a fiber woven fabric, a solvent polyurethane resin or an aqueous polyurethane resin emulsion is suitable as the adhesive. For example, when laminating and laminating a soft polyvinyl chloride resin on a fiber woven fabric, a paste-like soft polyvinyl chloride resin or an aqueous polyvinyl chloride resin emulsion is suitable as the adhesive. For example, when laminating and laminating a polyolefin-based resin on a fiber woven fabric, a solvent-based polyurethane resin (isocyanate curing type) or an aqueous ethylene-vinyl acetate-maleic acid copolymer resin emulsion is suitable as the adhesive. . The method of applying these adhesives is not particularly limited, but gravure coating is preferred for solvent-based adhesives and dip-nip is preferred for aqueous emulsion adhesives. The amount of the adhesive applied is desirably set in consideration of the feeling of the glittering composite film material to be obtained.

As another method of forming a glittering resin coating layer on the surface of a fiber woven fabric, a resin solution in which a thermoplastic resin is solubilized or dispersed in an organic solvent, or a thermoplastic resin emulsified in water. A resin-containing solution, such as a (polymerized) or suspended (polymerized) resin emulsion and a dispersion, was cast on a release film (paper) to form a film (based on 100 parts by weight of the thermoplastic resin). ) Pearl pigments containing silver white mica titanium and / or chromatic mica iron oxide as dichroic interference mica titanium or 70 to 99% by weight of dichroic interference mica titanium and the remaining component of less than 1 to 30% by weight While the glittering resin coating layer film containing 0.5 to 10 parts by weight of the composition and the release film (paper) are integrated with each other, the film forming surface and the fiber knitted woven fabric are thermocompressed. Te, after integrating the fabric and film forming film woven fibers knitted, can also be carried out by separating the release film. Thermoplastic resins suitable for use after being dissolved in an organic solvent include soft polyvinyl chloride resins, polyurethane resins, ethylene-vinyl acetate copolymer resins, and ethylene- (meth) acrylic acid (ester) copolymers. Coalescing resin, acrylic copolymer resin,
Styrene-based copolymer resins, polyester-based copolymer resins, polyamide-based copolymer resins, and the like. As the thermoplastic resin, a polyurethane resin is particularly preferably used from the viewpoints of transparency, resin strength, and flexibility of the film. Particularly, in the case of a soft polyvinyl chloride resin, a paste-type polyvinyl chloride resin can be used in the form of a plastisol to form a film by heat gelation. Thermoplastic resins that can be used in a water-dispersed state such as resin emulsions and dispersions include soft polyvinyl chloride resins, polyurethane resins, ethylene-vinyl acetate copolymer resins, and ethylene- (meth) acrylic acid (ester). ) Copolymer ionomer resins, acryl-based copolymer resins, styrene-based copolymer resins, polyester-based copolymer resins, polyamide-based copolymer resins, and the like. As the thermoplastic resin, a polyurethane resin is particularly preferably used from the viewpoints of transparency, resin strength, and flexibility of the film.

On the surface of the glittering resin coating layer of the glittering composite film material of the present invention, the dichroic interference mica or titanium is 70 to 99% by weight.
A surface treatment is performed using a resin solution containing a pearl pigment containing silver white mica titanium and / or chromatic mica iron oxide as the remaining component of less than 1 to 30% by weight, and further providing a glitter resin outermost layer. You can also. As the resin solution, a resin solution in which a thermoplastic resin is solubilized or dispersed in an organic solvent, or a thermoplastic resin is emulsified (polymerized) in water
And a resin-containing solution such as a suspended or polymerized resin emulsion and a dispersion. In this resin solution, dichroic interference mica titanium is added in an amount of 0.1 to 100% by weight of the solid content of the thermoplastic resin. It can be obtained by mixing and uniformly dispersing 5 to 10 parts by weight. At this time, it is preferable in terms of visual effect that the dichroic interference mica titanium compounded in the resin solution has a different interference color from the dichroic interference mica titanium compounded in the glittering resin coating layer. Thermoplastic resins suitable for use after being dissolved in an organic solvent include soft polyvinyl chloride resins, polyurethane resins, ethylene-vinyl acetate copolymer resins, and ethylene- (meth) acrylic acid (ester) copolymers. Examples include a coalescing resin, an acrylic copolymer resin, a styrene copolymer resin, a polyester copolymer resin, and a polyamide copolymer resin. Examples of thermoplastic resins that can be used in a water-dispersed state such as a resin emulsion and a dispersion include soft polyvinyl chloride resins, polyurethane resins, ethylene-vinyl acetate copolymer resins, and ethylene-vinyl acetate resins.
Examples thereof include (meth) acrylic acid (ester) copolymer ionomer resin, acrylic copolymer resin, styrene copolymer resin, polyester copolymer resin, and polyamide copolymer resin.

The surface treatment of the resin solution is performed by, for example, a gravure coating method, a microgravure coating method, a comma coating method, a roll coating method, a reverse roll coating method, a bar coating method, a kiss coating method, a flow coating method, etc. It is preferable that the thickness of the outermost layer of the conductive resin is 5 to 100 μm. It is preferable that the glitter resin coating layer on which the glitter resin outermost layer is formed has a visible light transmittance of 25 to 85%. Further, the glittering composite film material through which the knitting structure of the present invention can be seen through has a thermoplastic resin coating layer not containing the pearl pigment on at least one surface of the fiber knitted woven fabric, and the surface of the thermoplastic resin coating layer The pearl pigment is added in an amount of 0.5 to 10 with respect to 100 parts by weight of the thermoplastic resin.
A glitter resin outermost layer having a thickness of 5 to 100 μm including a weight part may be formed. At this time, the pearl pigment is
It is preferable that the thermoplastic resin coating layer containing the dichroic interference mica titanium in an amount of 70 to 100% by weight based on the weight of the dichroic interference mica has the visible light transmittance of 25 to 85%. The thermoplastic resin coating layer containing no pearl pigment is 80 to 500 produced by the T-die extrusion method, the inflation method, the calendar method, the cast method, or the like.
It is preferably a μm film.

The brilliant resin coating layer of the brilliant composite film material of the present invention, which allows the woven structure to be seen through, may be mirror-embossed, but may be a bag, a fashion bag, a sports bag, a pass case, For wallet and other miscellaneous goods and their use as members, the glittering resin coating layer and the glittering resin outermost layer have irregularities on the glittering resin coating layer and glittering resin outermost layer from the viewpoint of the touch in practical use, the prevention of dirt, and the slipperiness. Preferably, it is formed. In particular, from the viewpoint of the visual effect, the glitter composite film material of the present invention, in which the weaving structure can be seen through, has a glitter resin outermost layer provided on the surface of the glitter resin coating layer, and a glitter resin coating layer, The interference colors of the dichroic interference mica titanium contained in the outermost layer of the glittering resin are preferably different from each other. The composite film material obtained by subjecting the composite film material to irregularities is preferable because it exhibits unexpectedness that the interference color changes depending on the observation direction. Concavo-convex patterning includes continuous patterns of regular geometric patterns (lines, dots, circles, triangles, diamonds, pyramids, etc.), continuous patterns of irregular irregular patterns (sandblasting, pear fabric, etc.), natural products Continuous pattern of imitation pattern engraving (wood grain, rock, animal skin <elephant, rhinoceros, ostrich>, reptile <lizard, snake>), continuous pattern of character engraving (alphabet, logo,
Symbol mark, trademark, etc.) and other inscriptions. The number of projections and depressions is different depending on the shape of the stamp in the continuous pattern of the regular geometric pattern stamp and the continuous pattern of the irregular irregular pattern stamp. And 100 to 1,000,000 per unit area (cm ² ) of the surface of the glitter resin outermost layer
, Preferably 500 to 100,000, more preferably 1,000 to 50,000.
Further, it is preferable that the height difference between the highest position of the convex portion and the lowest position of the concave portion adjacent thereto is 5 μm or more. Regarding the continuous pattern of imitation pattern engraving of natural products and the continuous pattern of character engraving, there is no particular limitation on the number of protrusions (recesses). It is preferable that the uneven structure is formed so that the knitting structure of the glittering composite film material of the present invention can be seen through the above range of conditions. In addition, as a method of forming the concavo-convex shape, the concavo-convex shape corresponding to the concavo-convex shape to be formed can be continuously performed by pressing with a metal roll whose surface is engraved. At this time, the metal roll side on which the uneven shape is engraved may be heated with a heater to form the unevenness while melting and softening the glittering resin coating layer and the glittering resin outermost layer. The softened glittering resin coating layer and the glittering resin outermost layer may be subjected to concave and convex shaping while being pressed by a metal roll whose surface is carved. In the glittering film material of the present invention, it is preferable from the viewpoint of production efficiency that the concavo-convex pattern is continuously formed immediately after the glittering resin coating layer and the glittering resin outermost layer are laminated by the hot-pressure lamination.

The glittering composite film material of the present invention, in which the knitting structure can be seen through, has a glittering resin coating layer and a backside thermoplastic resin layer formed on a fiber cloth. Flexible polyvinyl chloride resin, ethylene-vinyl acetate copolymer resin, ethylene- (meth) acrylic acid (ester) copolymer resin, acrylic resin elastomer, styrene resin elastomer, polyurethane resin elastomer, polyester resin elastomer, By being selected from a polyamide-based resin elastomer, a polyvinylidene fluoride-based resin elastomer, or the like, high-frequency welder fusion bonding can be performed. For thermoplastic resins having low polarity such as polyethylene resin, polypropylene resin, ethylene-α-olefin copolymer resin, and polyolefin resin elastomer, ethylene-vinyl acetate copolymer resin, ethylene- (meth) acrylic acid ( By blending an ester) copolymer resin or the like, high-frequency weldability can be imparted, which is preferable. High-frequency welder fusion refers to laminating two or more glitter composite film materials of the present invention or a part of another thermoplastic resin molded product that can be thermally fused with the glitter composite film material of the present invention.
Between the two electrodes (one electrode is a weld bar), applying a potential difference that oscillates at a high frequency (1 to 200 MHz) to the electrodes while pressing the weld bar to the joint, These overlapping portions are thermally fused and bonded by the molecular frictional heat of the thermoplastic resin generated in the applied portions.

[0043]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the scope of these examples. In the following Examples and Comparative Examples, measurement methods such as a lightness index L ^* value, a color difference ΔE value, and a light transmittance of a film material are as follows. (I) fiber fabric (yarns) and lightness L ^* values of the measured JIS Standard Z-8729 (CIE1976 color system) of lightness L ^* value of the bright resin coating layer, the spectral color difference meter JP7100F (JUKI
), The tristimulus values X, Y, and Z of the fiber cloth (yarn) and the glittering resin coating layer were measured, and “L ^* a ^* b ^*
L ^* = 116 (Y /
Y ₀ ) ^1/3 −16, a ^* = 500 [(X / X ₀ ) ^1/3 −
(Y / Y ₀ ) ^1/3 ], b ^* = 200 [(Y / Y ₀ ) ^1/3]
− (Z / Z ₀ ) ^1/3 ]. X ₀ , Y ₀ , and Z ₀ are tristimulus values of the standard light C used for illumination.

(II) A fiber cloth (thread) and a brilliant resin coating
Measurement of color difference ΔE value of coating layer Color of JIS standard Z-8729 (CIE1976 color system)
The difference ΔE value is calculated using a spectral colorimeter JP7100F (JUKI
Co., Ltd.) and fiber fabric (yarn) and brilliant resin
The tristimulus values X, Y, and Z of the coating layer were measured, and "L^* a^* b^* 
L specified in the “color system and color difference formula”^* = 116 (Y /
Y₀ )^1/3 -16, a^* = 500 [(X / X ₀ )^1/3 −
(Y / Y₀ )^1/3 ], B^* = 200 [(Y / Y₀ )^1/3 
− (Z / Z₀)^1/3 ΔE from each value of^* ab = [(ΔL^*
 )^Two + (Δa^* ) + (Δb^* )]^{1 / Two} I asked for it. X
₀ , Y₀ , Z₀ Is the tristimulus value of the standard light C used for illumination.
You.

(III) Measurement of Light Transmittance of Bright Resin Coating Layer The light transmittance (C light source) of JIS K-6714 was measured using a direct-read haze meter (Toyo Seiki Seisakusho Co., Ltd.). (IV) The coloring and brilliancy of the film material and the transparency of the knitted fabric were evaluated by visual observation.

Example 1 Ether polyurethane resin (trade name: Estane 54640: Shore hardness 85)
A: 100 parts by weight of Kyowa Hakko Kogyo Co., Ltd. and dichroic interference mica titanium (1) (trademark: Iliodin 215 rutile / red pearl: titanium dioxide coverage 47%: average particle size 10)
６０60 μm: 2.5 parts by weight by Merck Japan Ltd.
Montanic acid ester lubricant (trademark: Licowax-
E: 0.2 parts by weight of Clariant Japan Co., Ltd.
0.1 parts by weight of a benzotriazole type ultraviolet absorber (trade name: Biosorb 510: Kyodo Yakuhin Co., Ltd.) and a hindered phenol antioxidant (trade name: Irganox 10)
10: A compound containing 0.1 part by weight of Ciba Specialty Chemicals Co., Ltd. was uniformly melted and kneaded for 4 minutes with a Banbury mixer set at 140 ° C.
After uniformly kneading with a hot roll (two rolls) set at 5 ° C. for 3 minutes, a milky white polyurethane resin film having a visible light transmittance of 67% and a 0.25 mm thickness was formed from this kneaded composition by calender rolling. Then the polyurethane resin film dyed black lightness index L ^* value is 27.1, and and the following polyester multifilament plain weave fabric having been subjected to adhesion treatment (thread density: warp 1500 denier (1666.
6dtex 288f non-twisted flat yarn) 12 / in × weft 15
00 denier (1666.6 dtex 288f non-twisted flat yarn) 12 yarns / in: porosity 10.8%: mass 145 g /
m ² ) and bonded together by thermocompression bonding with a laminator set at 160 ° C. to a thickness of 0.45 mm and a mass of 482 g / m.
² composite membrane materials were obtained. The lightness index L ^* value of the polyurethane resin layer of this composite film material was 33.0, and the dye ΔE value with the black dyed polyester multifilament plain fabric was 1
3.9. The appearance of the composite membrane material obtained in Example 1 was such that the beautiful knitted structure of the black dyed polyester multifilament plain fabric and the hairline could be seen through, and at the same time it had a red metallic coloring property. Moreover, when the object was picked up and observed, the metallic color development of red simultaneously exhibited the characteristic that the intensity of the degree of color development varied depending on the observation angle.

<Dyeing treatment of polyester multifilament plain fabric> Disperse dye (trade name: Miketon Pol)
Yester Black RBSF: Mitsui Toatsu Dyeing Co., Ltd.) Dip the polyester multifilament plain fabric in a dye bath (pH 5, 60 ° C) containing 3 g / l, dispersant 1 g / l, and leveling agent 1 g / l. The bath temperature was raised to 120 ° C., and the dyeing treatment was performed for 60 minutes. Next, soaping is performed for 10 minutes in warm water (70 ° C.) to which 1 g / l of a detergent has been added.
It was dried in a hot air drying oven at 120 ° C. for 2 minutes to obtain a polyester multifilament plain fabric dyed black (brightness index L ^* value: 27.7).

<Adhesion treatment of black dyed polyester multifilament plain woven fabric> A polyurethane resin emulsion (trade name: RU-40-350: polycarbonate system: solid content 35% by weight: Avicia Co., Ltd.) was diluted with water to obtain a solid content concentration. The black dyed polyester multifilament plain fabric is immersed in the polyurethane resin emulsion adjusted to 3.5%, the polyurethane resin impregnated black dyed polyester multifilament plain fabric is pulled up, and at the same time, squeezed with a nip roll to remove excess emulsion. The substrate was dried for 2 minutes in a hot air drying oven set at a temperature of ° C. The solid content is 1.
It was 4 g / m ² .

Example 2 The thermoplastic resin layer of the ether-based polyurethane resin of Example 1 was applied to a milky white soft polyvinyl chloride resin film having a visible light transmittance of 68% and a thickness of 0.25 mm having the following composition. changed. Otherwise the same as in Example 1, thickness 0.45 mm, mass 515
g / m ² of the composite membrane material was obtained. The brightness index L ^* of the glittering resin coating layer made of the soft polyvinyl chloride resin of the composite film material
The value was 31.7, and the color difference ΔE value from the plain fabric was 1
5.0. The appearance of the obtained composite membrane material was such that it had a beautiful knitted structure of a black-dyed polyester multifilament plain woven fabric, and was capable of seeing through a hairline, and at the same time, had a red metallic coloring property. Moreover, when the object was picked up and observed, the metallic color development of red simultaneously exhibited the characteristic that the intensity of the degree of color development varied depending on the observation angle.

<Soft Polyvinyl Chloride Resin Film> Trademark: S-1001: Kanebuchi Chemical Industry Co., Ltd .: 100 parts by weight of straight PVC (degree of polymerization: 1000) Trademark: Sansosizer DOP: Shin Nippon Rika Co., Ltd .: Plastic 60 parts by weight Trademark: Iriodin 215 rutile / red pearl: titanium dioxide coverage 47%, average particle size 10 to 60 μm, 2.5 parts by weight, manufactured by Merck Japan K.K.Trademark: Adecaizer O-130P: Asahi Denka Kogyo ( Co., Ltd .: Epoxidized soybean oil 4 parts by weight Trademark: ADK STAB AC-169: Asahi Denka Kogyo Co., Ltd .: Ba-Zn stabilizer 2 parts by weight Trademark: SZ-1: Sakai Chemical Industry Co., Ltd .: Zn-St type Metal soap 0.2 parts by weight Trademark: Biosorb 510: Kyodo Yakuhin Co., Ltd .: 0.3 parts by weight of benzophenone-based ultraviolet absorber Trademark: Tinuvin 770: Ciba Speci 0.2% by weight of Jalti Chemicals Co., Ltd.

Example 3 On the back surface of the composite film material obtained in Example 1, an ether-based polyurethane resin (trade name: Est
ane54640: Shore hardness 85A: 100 parts by weight of Kyowa Hakko Kogyo Co., Ltd., 2 parts by weight of a black pigment (HSM5078 black: carbon black content: 35% by weight: Hihiro Bix Co., Ltd.) and white pigment (HSM9050 white: dioxide) Titanium content 70% by weight: 1 part by weight of Nichiro Bix Co., Ltd., montanic acid ester lubricant (trademark:
Licowax-E: Clariant Japan Co., Ltd.
And 0.2 parts by weight of a benzotriazole-based ultraviolet absorber (trade name: Biosorb 510: Kyodo Yakuhin Co., Ltd.).
1 part by weight, hindered phenolic antioxidant (trademark:
Irganox 1010: A dark gray polyurethane resin film 0.25 mm thick obtained by the same film production method as in Example 1 from a compound containing 0.1 part by weight of Ciba Specialty Chemicals Co., Ltd. And thickness 0.66mm, mass 702g / m
² composite membrane materials were obtained. Lightness L ^* value of the surface polyurethane resin layer of the composite film material is 33.0, and the color difference ΔE value between blackening polyester multifilament plain weave fabric was 13.9. In addition, the brightness resin L ^* value of the glittering resin coating layer laminated and adhered to the 10.8% porosity portion of the knitted fabric tissue of the black dyed polyester multifilament was 44.2. The appearance of the composite membrane material obtained in Example 3 was such that the beautiful knitting and weaving structure of the polyester multifilament plain woven fabric and the hairline could be seen through, and at the same time, it had red metallic coloring. Further, in the composite film material of Example 3, the color of the void portion of the fiber cloth had a reddish purple metallic color developability at the same time. In addition, when picked up and observed, the metallic color development of red and purple is observed at the same time, and the degree of color development changes depending on the angle of observation, such as the effect that the fiber knitted fabric structure looks more three-dimensional. Demonstrated.

Example 4 A soft polyvinyl chloride resin compound having the following composition 1 was uniformly melt-kneaded with a Banbury mixer set at 140 ° C. for 4 minutes, and then mixed with a hot roll (two rolls) set at 165 ° C. The mixture was uniformly kneaded for one minute, and from this kneaded composition, a 0.20 mm thick soft polyvinyl chloride resin film (transparent colored thermoplastic resin layer film) having a visible light transmittance of 65% was calendered and rolled. Next, this transparent colored thermoplastic resin layer film was subjected to a lightness index L
^* One side of the same polyester multifilament plain fabric as in Example 1 dyed black with a value of 27.7
They were bonded together by thermocompression bonding using a laminator set at 60 ° C. Next, a 0.20 mm thick flexible polyvinyl chloride resin film having a visible light transmittance of 67% (brilliant resin coating layer film) was obtained from the flexible polyvinyl chloride resin compound having the following composition 2 by calendering under the same conditions as described above.
This was thermocompression-bonded with a laminator set at 160 ° C. on a transparent colored thermoplastic resin layer film layer having the following composition 1 and bonded to each other to have a thickness of 0.56 mm and a mass of 645 g / m ^2.
Was obtained. The brightness index L ^* value of the brilliant resin coating layer film layer 2 of this composite film material was 29.3, and the color difference ΔE from the black-dyed polyester multifilament plain fabric.
The value was 14.9. The appearance of the composite film material obtained in Example 4 was such that the beautiful knitted structure of the black-dyed polyester multifilament plain fabric and the hairline could be seen through, and at the same time, it had a red metallic coloring property. Further, the color development of the void portion 10.8% of the fiber cloth has a blue metallic coloring property at the same time, and when picked up and observed, this red metallic coloring changes between red and blue coloring depending on the observation angle. It has a mysterious visual effect that alternates.

<Soft Polyvinyl Chloride Resin Film 1: Transparent Colored Thermoplastic Resin Layer Film> Trademark: S-1001: Kanebuchi Chemical Industry Co., Ltd .: 100 parts by weight of straight PVC (degree of polymerization: 1000) Trademark: Sansosizer DOP : Shin Nippon Rika Co., Ltd .: 60 parts by weight of plasticizer Trademark: HSM9602 Blue: Nippon Bix Co., Ltd .: 2 parts by weight of ultramarine blue content: 5% by weight Chemical Soybean Oil 4 parts by weight Trademark: ADK STAB AC-169: Asahi Denka Kogyo Co., Ltd .: Ba-Zn based stabilizer 2 parts by weight Trademark: SZ-1: Sakai Chemical Industry Co., Ltd .: Zn-St type metal soap 0. 2 parts by weight Trademark: Biosorb 510: Kyodo Yakuhin Co., Ltd .: Benzophenone UV absorber 0.3 part by weight Trademark: Tinuvin 770: Ciba Specialty Chemical Ltd. 0.2 parts by weight

<Soft Polyvinyl Chloride Resin Film 2: Bright Resin Coating Layer Film> Trademark: S-1001: Kanebuchi Chemical Industry Co., Ltd .: 100 parts by weight of straight PVC (degree of polymerization: 1000) Trademark: Sansocizer DOP: Shin Nippon Rika Co., Ltd .: Plasticizer 60 parts by weight Trademark: Iliodin 215 rutile / red pearl: Titanium dioxide coverage 47%: Average particle size 10-60 μm: Merck Japan K.K. 2.5 parts by weight Trademark: Adecaizer O -130P: Asahi Denka Kogyo Co., Ltd .: Epoxidized soybean oil 4 parts by weight Trademark: ADK STAB AC-169: Asahi Denka Kogyo Co., Ltd .: Ba-Zn based stabilizer 2 parts by weight Trademark: SZ-1: Sakai Chemical Industry Co., Ltd. Co., Ltd .: 0.2 parts by weight of Zn-St-based metal soap Trademark: Biosorb 510: Kyodo Yakuhin Co., Ltd .: 0.3 parts by weight of benzophenone-based ultraviolet absorber Tinuvin 770: Ciba Specialty Chemicals Co., Ltd., 0.2 parts by weight

Example 5 A soft polyvinyl chloride resin compound having the following composition 3 was uniformly melt-kneaded with a Banbury mixer set at 140 ° C. for 4 minutes, and then mixed with a hot roll (two rolls) set at 165 ° C. The mixture was uniformly kneaded for 1 minute, and a soft polyvinyl chloride resin film (brilliant resin coating layer film) having a visible light transmittance of 61% and a thickness of 0.20 mm was calendered and roll-molded from the kneaded composition. Next, this brilliant resin coating layer film was obtained with a lightness index L ^* value of 27.
The same polyester multifilament plain woven fabric as in Example 1, which was dyed black, that is, No. 7, was bonded by thermocompression bonding with a laminator set at 160 ° C. Next, a soft polyvinyl chloride resin film (transparent colored thermoplastic resin layer film) having a visible light transmittance of 64% and a thickness of 0.20 mm was obtained from the soft polyvinyl chloride resin compound having the following composition 4 by calendering under the same conditions as described above. This was adhered by thermocompression bonding with a laminator set at 160 ° C. on a glittering resin coating layer film layer having the following composition 3 to obtain a composite film material having a thickness of 0.56 mm and a mass of 645 g / m ² . . The brightness index L ^* value of the glitter resin coating layer film 3 having the transparent coloring thermoplastic resin layer of this composite film material is 24.
5, and the color difference ΔE from the black-dyed polyester multifilament plain fabric was 15.2. The appearance of the composite membrane material obtained in Example 5 was such that the beautiful knitted structure of the black dyed polyester multifilament plain woven fabric and the hairline could be seen through, and at the same time, it had blue metallic coloring. In addition, the void portion 10.8 of the fiber cloth
The color development of the% portion has a red metallic coloring property at the same time,
When observed by hand, the metallic blue color exhibited a mysterious visual effect in which the blue and red colors alternated depending on the viewing angle.

<Soft Polyvinyl Chloride Resin Film 3: Glitter Resin Coating Layer Film> Trademark: S-1001: Kanebuchi Chemical Industry Co., Ltd .: 100 parts by weight of straight PVC (degree of polymerization: 1000) Trademark: Sansocizer DOP: Shin Nippon Rika Co., Ltd .: Plasticizer 60 parts by weight Trademark: Iriodin 225 rutile blue pearl: Titanium dioxide coverage 52%: Average particle size 10-60 μm: 2.5 parts by weight Merck Japan K.K. -130P: Asahi Denka Kogyo Co., Ltd .: Epoxidized soybean oil 4 parts by weight Trademark: ADK STAB AC-169: Asahi Denka Kogyo Co., Ltd .: Ba-Zn based stabilizer 2 parts by weight Trademark: SZ-1: Sakai Chemical Industry Co., Ltd. Co., Ltd .: 0.2 parts by weight of Zn-St-based metal soap Trademark: Biosorb 510: Kyodo Yakuhin Co., Ltd .: 0.3 parts by weight of benzophenone-based ultraviolet absorber Tinuvin 770: Ciba Specialty Chemicals Co., Ltd., 0.2 parts by weight

<Soft Polyvinyl Chloride Resin Film 4: Transparent Colored Thermoplastic Resin Layer Film> Trademark: S-1001: Kanebuchi Chemical Industry Co., Ltd .: 100 parts by weight of straight PVC (degree of polymerization: 1000) Trademark: Sansocizer DOP : Shin Nippon Rika Co., Ltd .: Plasticizer 60 parts by weight Trademark: HSM9152 Red: Hirobics Co., Ltd .: Perylene content 2.5% by weight: 2 parts by weight Trademark: ADEKASIZER O-130P: Asahi Denka Co., Ltd .: Epoxidized soybean oil 4 parts by weight Trademark: ADK STAB AC-169: Asahi Denka Kogyo Co., Ltd .: Ba-Zn stabilizer 2 parts by weight Trademark: SZ-1: Sakai Chemical Industry Co., Ltd .: Zn-St type Metal soap 0.2 parts by weight Trademark: Biosorb 510: Kyodo Yakuhin Co., Ltd .: 0.3 parts by weight of benzophenone-based ultraviolet absorber Trademark: Tinuvin 770: Ciba Specialty Chemicals Ltd. 0.2 parts by weight

Example 6 An ether-based polyurethane resin (trade name: Estane 54640: Shore hardness 85)
A: 100 parts by weight of Kyowa Hakko Kogyo Co., Ltd. and dichroic interference mica titanium (1) (trademark: Iliodin 215 rutile / red pearl: titanium dioxide coverage 47%: average particle size 10)
６０60 μm: 2.5 parts by weight by Merck Japan Ltd.
Montanic acid ester lubricant (trademark: Licowax-
E: 0.2 parts by weight of Clariant Japan Co., Ltd.
0.1 parts by weight of a benzotriazole type ultraviolet absorber (trade name: Biosorb 510: Kyodo Yakuhin Co., Ltd.) and a hindered phenol antioxidant (trade name: Irganox 10)
10: A compound containing 0.1 part by weight of Ciba Specialty Chemicals Co., Ltd. was uniformly melted and kneaded for 4 minutes with a Banbury mixer set at 140 ° C.
After uniformly kneading with a hot roll (two rolls) set at 5 ° C. for 3 minutes, a milky white polyurethane resin film having a visible light transmittance of 67% and a 0.25 mm thickness was formed from this kneaded composition by calender rolling. Next, this polyurethane resin film was coated with a carbon fiber plain woven fabric (2 ^* ) having a lightness index L ^* of 22.8.
000dtex (1800 denier) filament number 30
00: yarn density warp (untwisted flat yarn) 12.5 yarns / in × weft (untwisted flat yarn) 12.5 yarns / in: porosity 8.5%:
One side of a mass of 200 g / m ² ) was bonded by thermocompression bonding using a laminator set at 160 ° C. to obtain a composite membrane material having a thickness of 0.45 mm and a mass of 486 g / m ² . Lightness L ^* value of the polyurethane resin layer of the composite film material is 34.3,
The color difference ΔE from the carbon fiber plain fabric was 15.6. The appearance of the composite membrane material obtained in Example 1 was such that the beautiful weave structure of the carbon fiber plain woven fabric and the hairline could be seen through, and at the same time, it had a red metallic coloring property. Moreover, when the object was picked up and observed, the metallic color development of red simultaneously exhibited the characteristic that the intensity of the degree of color development varied depending on the observation angle.

<Adhesion treatment of carbon fiber plain fabric> Polyurethane resin emulsion (trade name: RU-40-350: polycarbonate type: solid content 35% by weight: Avicia Co., Ltd.)
The carbon fiber plain fabric is immersed in a polyurethane resin emulsion prepared by diluting water with water to a solid content concentration of 3.5%, and the polyurethane resin-impregnated carbon fiber plain fabric is pulled up and simultaneously squeezed with a nip roll to remove excess emulsion. Then, it was dried in a hot air drying oven set at 120 ° C. for 2 minutes. The solids adhesion amount was 1.4 g / m ² .

Example 7 The same 0.25 mm thick milky white polyurethane resin film having a visible light transmittance of 67% as in Example 6 was thermocompression-bonded to the back of the film material of Example 6 in the same manner as in Example 6. Then, a composite film material having a glittering resin coating layer on both sides of a carbon fiber plain woven fabric having a thickness of 0.70 mm and a mass of 770 g / m ² was obtained. The brightness index L ^* value of the brilliant resin coating layer of the composite film material made of polyurethane resin is 3
4.3, and the color difference ΔE value from the carbon fiber plain fabric is 1
5.6. The appearance of the composite membrane material obtained in Example 2 was such that the beautiful weave structure of the carbon fiber plain woven fabric and the hairline were visible, and at the same time, the composite membrane material had red metallic coloring. Also, when you pick it up and observe it,
This red metallic coloring simultaneously exhibited the feature that the intensity of the coloring varies depending on the observation angle.

Example 8 Dichroic interference mica titanium (1) of Example 6 (trade name: Iliodin 215 rutile / red pearl: titanium dioxide coverage 47%: average particle size 10 to 60)
μm: 2.5 parts by weight of Merck Japan K.K., dichroic interference mica titanium (2) (trademark: Iriodin 225 rutile blue pearl: titanium dioxide coverage 52%: average particle size 10 to 60 μm: Merck Japan Co., Ltd. was changed to 2.5 parts by weight to obtain a milky white polyurethane resin film having a visible light transmittance of 65% and a thickness of 0.25 mm. Example 6
Knitted plain weave of carbon fiber yarn and aramid fiber yarn (<carbon fiber yarn> 2000 dtex (180
0 denier) Filament number 3000: yarn density warp (untwisted flat yarn) 6.2 / in × weft (untwisted flat yarn) 6.2
Book / in: <Aramid fiber yarn> Trademark: Kevlar 49:
1420 denier (1577 dtex: yarn density warp (untwisted flat yarn) 6.2 yarns / in × weft (untwisted flat yarn) 6.2 yarns / in: * Both carbon fiber yarn and aramid fiber yarn are used for warp and weft. Were laid alternately and woven: the same as Example 1 except that the porosity was 8.5% and the mass was 180 g / m ^{2. The} thickness was 0.50 mm and the mass was 468 g / m ^2.
Was obtained. Brightness index L of the brilliant resin coating layer (carbon fiber thread portion) of this composite film material with polyurethane resin
^* Value is 31.2 and carbon fiber yarn (brightness index L
^* Color difference ΔE value between the value 23.4) 14.9, the color difference ΔE value of aramid fiber yarns (psychometric lightness L ^* value 77.3) was 4.4. The external appearance of the composite membrane material obtained in Example 3 was such that the beautiful weave structure of the carbon fiber plain woven fabric and the hairline could be seen through, and at the same time, the glittering resin coating layer laminated on the carbon fiber yarn was It had a blue metallic color. Further, when the object was picked up and observed, this blue metallic color exhibited the characteristic that the intensity of the color change varied depending on the angle of observation. In particular, Example 3
In the composite film material, the mixed weave pattern of the carbon fiber yarns and the aramid fiber yarns arranged alternately became clearer due to the metallic coloring effect.

Example 9 The same 0.25 mm thick milky white polyurethane resin film having a visible light transmittance of 67% as in Example 6 was thermocompression-bonded to the back of the film material of Example 8 in the same manner as in Example 6. Then, a composite film material having a glittering resin coating layer on both sides of a mixed woven plain fabric having a thickness of 0.75 mm and a mass of 750 g / m ² was obtained. The brightness index L ^* value of the bright resin coating layer (carbon fiber thread portion) of the surface of the film material with the polyurethane resin is 34.3, and the color difference Δ from the carbon fiber thread is
The E value was 15.6. The brightness index L ^* value of the glittering resin coating layer (carbon fiber yarn portion) made of the back surface polyurethane resin is 31.2, and the color difference ΔE value from the carbon fiber yarn is 1
4.9. In addition, a glittering resin coating layer made of a polyurethane resin on the surface of the composite film material (aramid fiber thread portion)
Has a lightness index L ^* of 72.4 and a color difference ΔE from the aramid fiber yarn of 3.6. Glitter resin coating layer of polyurethane resin on the back side (Aramid fiber thread)
Has a lightness index L ^* of 70.5 and a color difference ΔE from the aramid fiber yarn of 4.5. The appearance of the composite membrane material obtained in Example 9 was such that the beautiful weave structure of the carbon fiber plain woven fabric and the hairline could be seen through, and at the same time, the brilliancy due to the surface polyurethane resin laminated on the carbon fiber yarns The resin coating layer developed a blue metallic color and the back surface developed a red metallic color. Further, when the object was picked up and observed, this blue metallic color exhibited the characteristic that the intensity of the color change varied depending on the angle of observation. In particular, in the composite film material of Example 9, the mixed woven pattern of the carbon fiber yarns and the aramid fiber yarns arranged alternately became clearer due to the metallic coloring effect.

Example 10 Dichroic interference mica of Example 6
Titanium (1) (trademark: Iliodin 215 Rutile Red)
Pearl: titanium dioxide coverage 47%: average particle size 10-6
0 μm: 2.5 parts by weight of Merck Japan Co., Ltd.
Chromatic interference mica titanium (3) (trademark: Iriodin 235L)
Chill Green Pearl: Titanium dioxide coverage 57%: flat
Average particle size 10 to 60 μm: Merck Japan K.K.
Changed to 5 parts by weight, visible light transmittance of 0.25 mm thickness 63%
To obtain a milky white polyurethane resin film. Also implemented
Of a blended plain weave of carbon fiber yarn and aramid fiber yarn of Example 8
Except that the aramid fiber yarn was dyed dark blue with acid dye.
Same as Example 8, thickness 0.50 mm, mass 468 g / m
^Two Was obtained. Polyurethane resin of this composite membrane
Index of brilliant resin coating layer (carbon fiber thread part)
L^* The value was 31.7 and the carbon fiber yarn (brightness index)
L^* Color difference ΔE value from the value 23.4) is 14.1, aramid
Fiber yarn (brightness index L^* The value of the color difference ΔE from the value 36.8) is
12.4.

<Dyeing treatment of aramid fiber yarn> Acid dye (tradename: Elionyl Blue Blue RL)
200%: Ciba Specialty Chemicals Co., Ltd. 2
g / l, acid dye (trademark: Lanacron Blac)
k SR: Ciba Specialty Chemicals Co., Ltd. 1
g / l, dispersant 1 g / l, leveling agent 1 g / l, carrier 3 g / l, a mixed woven plain woven fabric of carbon fiber yarn and aramid fiber yarn in a dye bath (pH 5.5, 60 ° C.). After immersion, the dyeing bath was heated to 110 ° C., and the dyeing treatment was performed for 60 minutes. Next, soaping was performed for 10 minutes in warm water (70 ° C.) to which 1 g / l of a detergent was added. And dried in a hot air drying oven at 120 ° C. for 2 minutes to obtain an aramid fiber yarn (lightness index L ^* value 36.8) dyed in dark blue. The appearance of the composite membrane material obtained in Example 5 was such that the beautiful knitting structure of the mixed woven plain fabric and the hairline could be seen through, and the polyurethane resin layer was formed on the carbon fiber yarn and the aramid fiber yarn. Each had a different green metallic color. In addition, when they were picked up and observed, the different green metallic colors simultaneously exhibited the characteristic that the intensity of the color changes depending on the viewing angle. In particular, in the composite film material of Example 10, the blended pattern of the carbon fiber yarns and the aramid fiber yarns alternately arranged had a calm gradation appearance due to green metallic coloring.

[Embodiment 11] The same 0.25 mm thick visible light transmittance of 67% as that of Embodiment 6 was formed on the back surface of the film material of Embodiment 10.
The milky white polyurethane resin film was bonded by thermocompression bonding according to the same method as in Example 6 to have a thickness of 0.75 mm.
A composite film material having a glittering resin coating layer on both surfaces of a mixed woven plain woven fabric having a mass of 750 g / m ² was obtained. The brightness index L ^* value of the brilliant resin coating layer (carbon fiber thread portion) made of the surface polyurethane resin of this composite film material was 31.7, and the color difference ΔE value from the carbon fiber thread was 15.6. . The brightness index L ^* value of the glittering resin coating layer (carbon fiber thread portion) made of the back surface polyurethane resin is 31.2, and the color difference Δ from the carbon fiber thread is
The E value was 14.1. The brightness index L ^* value of the glitter resin coating layer (aramide fiber yarn portion) of the surface of the composite film material made of polyurethane resin was 44.8, and the color difference ΔE value from the aramid fiber yarn was 7.6. there were. The brightness index L ^* value of the glittering resin coating layer (aramid fiber yarn portion) made of the back polyurethane resin was 42.1, and the color difference ΔE value from the aramid fiber yarn was 7.9. Example 11
The appearance of the composite membrane material obtained in the above, the beautiful knitting structure of the mixed weave plain fabric and the hairline can be seen through, and at the same time, the polyurethane resin layer on the surface is on the carbon fiber yarn and the aramid fiber yarn respectively. A different green metallic color was formed, and the glittering resin coating layer of the polyurethane resin on the back surface formed a different red metallic color on the carbon fiber yarn and the aramid fiber yarn, respectively. In addition, when they were picked up and observed, the different green metallic colors simultaneously exhibited the characteristic that the intensity of the color changes depending on the viewing angle. In particular, in the composite membrane material of Example 11, the mixed weave pattern of the carbon fiber yarns and the aramid fiber yarns alternately arranged has a calm gradation appearance due to the green metallic coloring on the front surface and the red metallic coloring on the back surface. became.

[0066] Example 12 Carbon fiber plain weave fabric of Example 6 (2000 dtex (1800 denier) filament number 3000: Yarn Density warp (untwisted flat yarn) 12.5 present / in
× 12.5 wefts (untwisted flat yarns) / in: porosity 8.5
%: Warp yarn density of mass 200 g / m ² ) 9.5 yarns / i
The nx weft yarn density was changed to 9.5 yarns / in. The porosity of the carbon fiber plain fabric is 31.5%, and the mass is 150%.
g / m ² . The same 0.25 mm thick milky white polyurethane resin film having a visible light transmittance of 67% as in Example 6 was bonded by thermocompression bonding to one surface of the carbon fiber plain woven fabric having the changed yarn density according to the same method as in Example 6. Was. Next, an ether-based polyurethane resin (trade name: Estane 54640: Shore hardness 85) is formed on the back surface of the composite film material.
A: 100 parts by weight of Kyowa Hakko Kogyo Co., Ltd., 3.5 parts by weight of an organic pigment (trade name: HSM9601 Blue: ultramarine blue content: 50% by weight: Nippon Bix Co., Ltd.), and a montanic acid ester lubricant ( Trademark: Licowax-E: 0.2 parts by weight of Clariant Japan K.K., 0.1 part by weight of benzotriazole-based ultraviolet absorber (trademark: Biosorb 510: Kyodo Yakuhin), hindered phenol-based oxidation Inhibitor (trademark: Irganox 1010: Ciba.
Specialty Chemicals Corporation) and compounded by the same procedure as in Example 6 from the compound of 0.25mm thick visible light transmittance of 6.7% 0.1 part by weight lightness index L ^*
A back surface polyurethane resin film having a value of 37.2 (brightness index L ^* value difference from carbon fiber plain woven fabric is 14.4) is bonded by thermocompression bonding to have a thickness of 0.70 mm and a mass of 686 g /
thermoplastic resin layers on both surfaces of the carbon fiber plain weave fabric of m ² (surface layer glitter resin coating layer, the back surface of the thermoplastic resin layer containing no pearl pigment) to obtain a composite film material having a. The brightness index L ^* value of the bright resin coating layer (carbon fiber thread portion) made of polyurethane resin of the composite film material was 34.3, and the color difference ΔE value from the carbon fiber plain fabric was 15.6. Was. Further, the brightness index L ^* value of the glittering resin coating layer laminated and adhered to the 31.5% porosity portion of the knitted tissue structure of the carbon fiber plain woven fabric is 48.2.
Met. The appearance of the composite membrane material obtained in Example 12 was such that the beautiful weave structure of the carbon fiber plain woven fabric and the hairline could be seen through, and at the same time, the composite film had a red metallic coloring property. Further, in the composite film material of Example 12, the color development in the void portion of the fiber cloth had purple metallic coloring property at the same time. Also, when observed by hand, the red and purple metallic colors simultaneously exhibited the characteristic that the intensity of the color changes depending on the viewing angle.

Example 13 The thermoplastic resin of Example 6
(Ether-based polyurethane resin)
Titanium mica (1) (trademark: Iriodin 215 rutile)
Red Pearl: titanium dioxide coverage 47%: average particle size 1
0 to 60 μm: 2.5 parts by weight by Merck Japan Ltd.
0.5 parts by weight of the silver white mica titanium (trademark: Iri)
Ojin 153 Fresh Pearl: Titanium dioxide coverage
16%: average particle size 30-300 μm: Merck Japan
Example 6 except for replacing with 0.5 parts by weight.
And the same formulation. (Dichroic interference mica titanium: Silver cloud
Mother composition weight% ratio: 80:20)
0.45 mm thick, 486 g / mass
m ^Two Was obtained. Polyurethane tree of this composite membrane
Lightness index L of the brilliant resin coating layer composed of oil^* The value is 37.
7, and the color difference ΔE value from the plain carbon fiber fabric was 13.
It was 6. The appearance of the composite membrane material obtained in Example 8 was carbon.
Beautiful weaving structure of fiber plain fabric and see-through of hairline
Is possible and at the same time calm red metal
It had color development properties. Also pick up and observe
The red metallic color depends on the viewing angle.
Features that change the intensity of the color development
Commanded.

Example 14 The dichroic interference mica titanium (1) contained in the thermoplastic resin (ether polyurethane resin) layer of Example 6 (trade name: Iliodin 215 rutile)
Red Pearl: titanium dioxide coverage 47%: average particle size 1
0 to 60 μm: 0.5 part by weight of 2.5 parts by weight of Merck Japan K.K.
Average particle size 5 to 20 μm: Merck Japan K.K.
It was the same as Example 6 except that it was replaced by 5 parts by weight.
(Dichroic interference mica titanium: Composition weight% of colored mica iron oxide
Ratio 80:20) Except for this change, a composite membrane material having a thickness of 0.45 mm and a mass of 486 g / m ² was obtained in the same procedure as in Example 6. The brightness index L ^* value of the brilliant resin coating layer made of the polyurethane resin of the composite film material was 31.6, and the color difference ΔE value from the carbon fiber plain fabric was 16.5. The appearance of the composite membrane material obtained in Example 9 was such that it had a beautiful knitting and weaving structure of a plain carbon fiber woven fabric, was capable of seeing through hair lines, and had a calm red metallic coloring. Moreover, when the object was picked up and observed, the metallic color development of red simultaneously exhibited the characteristic that the intensity of the degree of color development varied depending on the observation angle.

Example 15 The composite film material of Example 6 was coated with a brilliant resin by using an embossing roll having an irregular type satin-finished continuous engraving with a height difference of 15 μm and irregularities of about 3000 / cm ^2. The same procedure as in Example 6 was carried out except that the embossing was performed immediately after the hot-press laminating step of the layer film, and the thickness was set to 0.
A composite membrane material having a size of 45 mm and a mass of 486 g / m ² was obtained. The brightness index L ^* value of the brilliant resin coating layer of this film material was 35.1, and the color difference ΔE value from the carbon fiber plain fabric was 16.6. The appearance of the composite membrane material obtained in Example 10 was such that the beautiful weave structure of the carbon fiber plain woven fabric and the hairline could be seen through, and at the same time, it had a soft red metallic coloring property. Moreover, when the object was picked up and observed, the metallic color development of red simultaneously exhibited the characteristic that the intensity of the degree of color development varied depending on the observation angle.

[Example 16] The carbon fiber plain fabric of Example 7 was converted to a triaxial plain fabric (a yarn density bias yarn of 750 denier (833 dtex)) composed of polyester multifilament yarn.
96f non-twisted flat yarn) 19 yarns (2 yarns) / in x weft 7
50 denier (833 dtex 96f non-twisted flat yarn) 19 yarns (two yarns aligned) / in: porosity 12%: mass 260 g / m
² ) The same procedure as in Example 6 was carried out except that the triaxial plain fabric was dyed black, and the thickness was 0.78 mm and the mass was 788 g /
A composite film material having a glittering resin coating layer on both sides of an m ² triaxial plain fabric was obtained. The brightness index L ^* value of the brilliant resin coating layer made of the polyurethane resin of the film material was 33.1, and the color difference ΔE value from the triaxial plain fabric was 15.2. The appearance of the composite membrane material obtained in Example 16 was such that the specific knitted structure of the triaxial plain woven fabric and the hairline could be seen through, and at the same time, it had red metallic coloring.
Moreover, when the object was picked up and observed, the metallic color development of red simultaneously exhibited the characteristic that the intensity of the degree of color development varied depending on the observation angle.

<Dyeing treatment of polyester fiber thread triaxial plain fabric> Disperse dye (trade name: Miketon Polyes)
ter Black RBSF: Mitsui Toatsu Dye Co., Ltd.
The polyester fiber thread triaxial plain fabric is immersed in a dye bath (pH 5, 60 ° C.) containing 3 g / l, a dispersant 1 g / l, and a leveling agent 1 g / l, and the dye bath is heated to 120 ° C. For 60 minutes. Then, warm water (7 g / l with 1 g / l of detergent) was added.
(0 ° C.) for 10 minutes, and dried in a hot air drying oven at 120 ° C. for 2 minutes to obtain a polyester fiber yarn triaxial plain fabric dyed black (brightness index L ^* value: 26.3).

[Example 17] The carbon fiber plain fabric of Example 9 was converted to a 4-axis plain fabric (a yarn density bias yarn of 500 denier (555 dtex)) composed of polyester multifilament yarn.
96f non-twisted flat yarn 13 yarns / in × 500 denier warp (555dtex 96f non-twisted flat yarn) 13 yarns / in × 500 denier weft (555dtex 96f non-twisted flat yarn) 13
Book / in: porosity 3.4%: mass 180 g / m ² ) The same as Example 6 except that this 4-axis plain fabric was dyed black, thickness 0.70 mm, mass 716 g / m 2 ² of 4
A composite film material having a glittering resin coating layer on both surfaces of the shaft flat fabric was obtained. Lightness index L of the polyurethane resin layer of this composite film material
^{* The} value was 31.7, and the color difference ΔE value from the 4-axis plain fabric was 14.2. The appearance of the composite membrane material obtained in Example 17 was such that the specific weaving structure of the 4-axis plain woven fabric and the hairline could be seen through, and at the same time, the composite membrane material had red metallic coloring. Also, when picked up and observed, this red metallic coloration depends on the viewing angle,
At the same time, the feature of changing the degree of color development was exhibited.

<Dyeing treatment of polyester fiber yarn 4-axis plain fabric> Disperse dye (trade name: Miketon Polyes)
ter Black RBSF: Mitsui Toatsu Dye Co., Ltd.
A polyester fiber yarn 4-axis flat fabric is immersed in a dye bath (pH 5, 60 ° C.) containing 3 g / l, a dispersant 1 g / l, and a leveling agent 1 g / l, and the dye bath is heated to 120 ° C. For 60 minutes. Then, warm water (7 g / l with 1 g / l of detergent) was added.
(0 ° C.) for 10 minutes, and dried in a hot air drying oven at 120 ° C. for 2 minutes to obtain a polyester fiber yarn 4-axis plain fabric (lightness index L ^* value: 26.0) dyed black.

Example 18 A dichroic interference mica titanium (3) (trade name: Iliodin 235 rutile green pearl: titanium dioxide) was applied to one side of a carbon fiber plain woven fabric having a lightness index L ^* value of 22.8 in Example 6. 57% coverage: average particle size 10-6
0 μm: Resin solution containing Merck Japan Co., Ltd.
A composite film material having a thickness of 0.45 mm and a weight of 486 g / m ² was obtained in the same manner as in Example 6 except that the outermost layer of the glittering resin was provided by applying and drying using a gravure roll having a 0-wire mesh. The lightness index L ^* value of the bright resin coating layer made of polyurethane resin of the composite film material is 30.7, glittering resin coating layer and the visible light transmittance of the bright resin outermost layer 54%
And the color difference ΔE value from the plain carbon fiber fabric is 13.3.
Met. The appearance of the composite membrane material obtained in Example 13 was such that when a red metallic coloring polyurethane resin layer was provided on a carbon fiber plain woven fabric that developed green color, the green fabric was observed by hand. The red metallic color and the red metallic color alternately change the intensity of the color development in accordance with the unevenness of the knitting structure, and at the same time exhibit the full of three-dimensional features.

<Gravure Coating Solution> Trademark: Takelac E-350: Takeda Pharmaceutical Co., Ltd .: 100% by weight of polyester-based polyurethane resin (solid content: 26% by weight, IPA, toluene solvent system) Trademark: Iliodin 235 rutile Green Pearl 5 parts by weight Diluent: 30 parts by weight of toluene

Example 19 On both surfaces of the film material of Example 7, dichroic interference mica titanium (2) (trade name: Iriodin 225 rutile blue pearl: titanium dioxide coverage: 52%: average particle size: 10 to 60 μm: Merck) Example 2 except that a resin solution containing Japan Co., Ltd. was applied and dried using an 80-line mesh gravure roll to provide a glitter resin outermost layer.
A composite film having a thickness of 0.70 mm and a mass of 770 g / m ² was obtained. The brightness index L ^* value of the glitter resin coating layer made of polyurethane resin of the composite film material was 29.5, the visible light transmittance of the glitter resin coating layer and the outermost layer of the glitter resin was 57%, and Color difference ΔE with carbon fiber plain fabric
The value was 12.6. The appearance of the composite film material obtained in Example 19 was such that, when the surface was treated with a blue metallic coloring surface treatment layer provided on the red-colored composite film material, when observed by hand, The color of the red metallic color simultaneously exhibited the feature full of a three-dimensional effect in which the intensity of the color change alternately changes according to the unevenness of the knitting structure.

<Gravure coating solution> Trade name: Takerac E-350: Takeda Pharmaceutical Co., Ltd .: 100 parts by weight of polyester-based polyurethane resin (solid content: 26 wt%, IPA, toluene solvent) Trade name: Iliodin 225 rutile blue pearl 5 parts by weight Diluent: 30 parts by weight of toluene

Example 20 A brilliant resin coating layer was formed on the composite film material of Example 18 by using an embossing roll having a pyramid-type continuous engraving with a height difference of 45 μm and projections of about 640 / cm ^2. A composite film material having a thickness of 0.45 mm and a mass of 486 g / m ² was obtained in the same manner as in Example 18, except that the outermost layer of the brilliant resin was subjected to the embossing. The lightness index L ^* value of the polyurethane resin layer of this composite film material was 32.6, the visible light transmittance of the glittering resin coating layer and the outermost layer of the glittering resin was 53%, and the light transmittance of the carbon fiber plain fabric was 53%. The color difference ΔE value is 1
7.4. The appearance of the composite membrane material obtained in Example 20 was such that the beautiful weave structure of the carbon fiber plain woven fabric and the hairline were visible, and at the same time, it had a vivid and complex red and green metallic coloring. Was. Further, when the object was picked up and observed, the metallic color development of red and green changed according to the angle of observation, and simultaneously exhibited the characteristic that the intensity of the coloration changed.

Example 21 Using the embossing roll having the unevenness of height of 80 μm and the continuous imprint of the image pattern on the composite film material of Example 19, embossing was performed on the glittering resin coating layer and the glittering resin outermost layer. A composite membrane material having a thickness of 0.45 mm and a mass of 486 g / m ² was obtained in the same manner as in Example 19 except that the coating was performed.
The lightness index L ^* value of the polyurethane resin layer of this composite film material was 33.9, the visible light transmittance of the glittering resin coating layer and the outermost layer of the glittering resin was 55%, and the light transmittance of the carbon fiber plain fabric was 55%. The color difference ΔE value was 16.5. The appearance of the composite membrane material obtained in Example 21 was such that the beautiful weave structure of the carbon fiber plain woven fabric and the hairline could be seen through, and at the same time, the composite film material had complex red and blue metallic coloring.
Also, when picked up and observed, the metallic color development of red and blue changed according to the viewing angle, and simultaneously exhibited the characteristic that the intensity of the color change was changed.

Example 22 Dichroic interference mica titanium (1) of Example 6 (trade name: Iliodin 215 rutile / red pearl: titanium dioxide coverage 47%: average particle size 10-6)
0 μm: A film containing 2.5 parts by weight of Merck Japan KK was changed to a milky white polyurethane resin film having a visible light transmittance of 73% and a thickness of 0.15 mm. Next, the dichroic interference mica titanium (2) of Example 3 (trade name: Iriodin 2)
25 rutile blue pearl: titanium dioxide coverage 52
%: Average particle size: 10 to 60 μm: A film containing 2.5 parts by weight of Merck Japan K.K. was changed to a milky white polyurethane resin film having a visible light transmittance of 74% and a thickness of 0.10 mm. Except for this, the film was the same as in Example 6, and the two films were laminated on one side of a carbon fiber plain fabric with the dichroic interference mica titanium (1) -containing film layer as the outermost layer side (visible light (Transmissivity: 58%) and bonded together to obtain a composite film having a thickness of 0.45 mm and a mass of 486 g / m ² . The appearance of the composite membrane material obtained in Example 17 was such that the beautiful weave structure of the carbon fiber plain woven fabric and the hairline could be seen through, and at the same time, the composite film had complex red and blue metallic coloring properties. Also, when picked up and observed, the metallic color development of red and blue changed according to the viewing angle, and simultaneously exhibited the characteristic that the intensity of the color change was changed.

Example 23 A dichroic interference mica titanium (2) (trade name: Iliodin 225 rutile blue pearl: titanium dioxide coverage: 52%) was applied to one surface of the carbon fiber plain fabric of the composite film material of Example 6. Average particle size 10 to 60 μm: Merck
A resin solution containing Japan Co., Ltd. was applied using a gravure roll of 80-wire mesh and dried to form a glittering resin coating layer. Next, the dichroic interference mica titanium (1) of Example 6 (trademark: Iliodin 2)
15 rutile red pearl: titanium dioxide coverage 47
%: Average particle size: 10 to 60 μm: a 0.25 mm thick milky white polyurethane resin film having a visible light transmittance of 67% containing 2.5 parts by weight of Merck Japan Co., Ltd. was laminated in the same manner as in Example 6. Then, a composite film having a thickness of 0.46 mm and a mass of 495 g / m ² was obtained. The appearance of the composite membrane material obtained in Example 23 was such that the beautiful knitting structure of the carbon fiber plain woven fabric and the hairline could be seen through, and at the same time, the composite material had complex red and green metallic coloring. Further, when the object was picked up and observed, the metallic color development of red and green changed according to the angle of observation, and simultaneously exhibited the characteristic that the intensity of the coloration changed.

<Gravure coating solution> Trade name: Takerac E-350: Takeda Pharmaceutical Co., Ltd .: Polyester polyurethane resin (solid content 26 wt%, IPA, toluene solvent system) 100 parts by weight Trade name: Iliodin 225 rutile blue pearl 10 parts by weight Diluent: 30 parts by weight of toluene

Example 24 A thermoplastic low-density polyethylene resin (1) (trade name: Kernel KF270: MFR2) obtained by polymerizing the thermoplastic resin layer composed of the ether-based polyurethane resin of Example 6 in the presence of a metallocene-based catalyst was used. 0.0: Density 0.907: 60 parts by weight of Nippon Polychem Co., Ltd. and ethylene-vinyl acetate copolymer resin (1) (trademark: Evatate K2010: MFR 3.0: VA content 25% by weight: Sumitomo Chemical Co., Ltd.) Dichroic interference mica titanium (1) (trademark: Iriodin 215 rutile / red pearl: titanium dioxide coating ratio: 47%: average particle size: 10)
６０60 μm, 2.5 parts by weight by Merck Japan Ltd.
1.0 part by weight of a phosphate ester lubricant (trademark: LTP-2: Kawaken Fine Chemical Co., Ltd.) and 0.3 part by weight of a benzotriazole ultraviolet absorber (trademark: Biosorb 510: Kyodo Yakuhin Co., Ltd.) 0.25 parts by weight of a hindered amine light stabilizer (trade name: Tinuvin 770: Ciba Specialty Chemicals Co., Ltd.)
It was changed to a milky white polyolefin-based resin film with a visible light transmittance of 65% of 65 mm. Otherwise in the same manner as in Example 6, a composite film having a thickness of 0.45 mm and a mass of 445 g / m ² was obtained. The brightness index L ^* value of the brilliant resin coating layer made of the polyolefin resin of the composite film material was 34.0, and the color difference ΔE value from the carbon fiber plain fabric was 15.8.
The appearance of the composite film material obtained in Example 24 was such that the beautiful knitting and weaving structure of the carbon fiber plain woven fabric and the hairline could be seen through, and at the same time, it had a red metallic coloring property. Moreover, when the object was picked up and observed, the metallic color development of red simultaneously exhibited the characteristic that the intensity of the degree of color development varied depending on the observation angle.

Comparative Example 1 A carbon fiber plain woven fabric having a lightness index L ^* value of 22.8 (2,000 dtex (1800)
11. Denier) number of filaments 3000: yarn density warp (untwisted flat yarn) 12.5 / in × weft (untwisted flat yarn)
5 yarns / in: porosity 8.5%: mass 200 g / m ² ) was converted to a plain woven fabric (yarn density warp 75
0 denier (833dtex 96f non-twisted flat yarn) 22 yarns (2 yarns) / in x weft 750 denier (830dte
x 96f non-twisted flat yarn) 22 yarns (two yarns aligned) / in: porosity 5.7%: mass 180 g / m ² : lightness index L ^* value 9
Except having changed to 2.5), it was the same as Example 6, and a composite membrane material having a thickness of 0.45 mm and a mass of 486 g / m ² was obtained. The lightness index L ^* value of the polyurethane resin layer of this composite film material is 9
0.3 and the color difference Δ
The E value was 3.2. The external appearance of the composite membrane material obtained in Comparative Example 1 was visible through the knitting structure and hair line of the polyester fiber plain woven fabric, but the polyester fiber plain woven fabric was intact and lacked in quality, and at the same time the appearance was brilliant. Was poor.

Comparative Example 2 The polyester polymer of Example 16
Triaxial flat woven fabric consisting of multifilament yarn (yarn density
Ass yarn 750 denier (833 dtex 96f untwisted flat
Yarn) 19 yarns (2 yarns) / in x 750 denier weft
(833dtex 96f non-twisted flat yarn) 19 (2 lines)
/ In: porosity 12%: mass 260 g / m^Two : Lightness index
L^* Example 6 except that the black staining of value 91.3) was omitted.
0.78mm, mass 788g / m^Two Duplication
A composite material was obtained. The brightness of the polyurethane resin layer of this composite film material
Degree index L ^* The value is 89.6 and the polyester fiber
The color difference ΔE value from the plain fabric was 3.1. Obtained in Comparative Example 2
The appearance of the composite membrane material is a three-axis plain weave structure and
Arline perspective was possible, but appearance was poor
Was something new.

Comparative Example 3 Dichroic interference mica titanium (1) of Example 6 (trade name: Iliodin 215 rutile / red pearl: titanium dioxide coverage 47%: average particle size 10 to 60)
[mu] m: 2.5 parts by weight of chromium mica iron oxide (trademark: Iriodin 520 bronze satin: iron oxide coverage: 44%: average particle size 5 to 20 [mu] m: Merck Japan KK) The same as Example 6 except that the weight was changed to 2.5 parts by weight, the thickness was 0.45 mm, and the mass was 486 g / m.
² composite membrane materials were obtained. The light transmittance of the polyurethane resin layer film used for the composite film material was 18%, and the lightness index L ^* value of the polyurethane resin layer of the composite film material was 68.1. Although the appearance of the composite film material obtained in Comparative Example 3 was excellent in bronze metallic coloration, the knitting structure of the carbon fiber plain fabric and the beautiful and delicate hair lines were completely hidden, and it was monotonous. And lacked interest.

Comparative Example 4 Dichroic interference mica titanium (1) of Example 6 (trade name: Iliodin 215 rutile / red pearl: titanium dioxide coverage 47%: average particle size 10 to 60)
μm: 2.5 parts by weight of an aluminum powder pigment (trade name: Alpaste P0100 Leafing Medium: water surface diffusion area: 15,000 g / m)
² : The same as in Example 6 except that the weight was changed to 2.5 parts by weight by Toyo Aluminum Co., Ltd., thickness 0.45 mm, mass 48
A composite membrane material of 6 g / m ² was obtained. The light transmittance of the polyurethane resin layer film used for the composite film material was 1.4%, and the lightness index L ^* value of the polyurethane resin layer of the composite film material was 78.4. The external appearance of the composite film material obtained in Comparative Example 4 was silver-gray in direct sunlight, but it was dull to a gray color under a weak indoor light source. Furthermore, the knitting structure of the carbon fiber plain woven fabric and the beautiful and delicate hair lines were completely hidden, and were monotonous and lacked in interest.

[0088]

According to the present invention, it is possible to obtain a composite film material which has not been obtained by the prior art but has a beautiful brilliant color while having the transparency of the knitted structure of the base fiber knitted fabric.
Moreover, as is clear from Examples 1 to 24, the visual effect is extremely high. Therefore, the brilliant composite film material of the present invention, which can be seen through the woven structure, can be suitably used for applications such as awning tents, covers, interior materials, decorative sheets, and other miscellaneous goods and their members. It can also be suitably used in applications as

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4L031 AB32 AB33 BA09 BA19 BA24 DA00 4L033 AA09 AB05 AB06 AC15 CA50 DA06 4L048 AA05 AA20 AA24 AB13 AC01 BC02 4L049 AA02 AA17 AA18 AB11 AB18 BA39 DA17 DA30

Claims (20)

[Claims] 1. A base fabric made of a fiber knitted and woven fabric, and a thermoplastic resin covering at least one surface of the base fabric.
0 parts by weight, and a glitter resin coating layer containing 0.5 to 10 parts by weight of pearl pigment, the fiber knitted fabric for the base cloth,
CI defined in JIS Z-8729-1980
It has a lightness index L ^* value of E1976 color system of 10 to 60, and the pearl pigment has a weight of 70 to 10
0% by weight of dichroic interference mica titanium, wherein the glittering resin coating layer has a visible light transmittance of 25 to 85% (JIS K
-6714-1988), wherein the woven structure of the fiber knitted woven fabric for the base fabric can be seen through and has brilliancy, wherein the woven structure can be seen through. 2. A base fabric made of a fiber knitted and woven fabric, and a thermoplastic resin covering at least one surface of the base fabric.
0 parts by weight and a glittering resin coating layer containing 0.5 to 10 parts by weight of a pearl pigment, and a glittering resin outermost layer is further formed on the surface of the glittering resin coating layer. The outermost layer of the hydrophilic resin contains 0.5 to 10 parts by weight of a pearl pigment having a different interference color from the pearl pigment contained in the glittering resin coating layer, based on 100 parts by weight of the thermoplastic resin. The fiber knitted woven fabric has a lightness index L ^* value of CIE1976 color system defined in JIS Z-8729-1980 of 1
Wherein the pearl pigment contains 70 to 100% by weight of the weight of the dichroic interference mica titanium, and the brilliant resin coating layer on which the brilliant resin outermost layer is formed is 25% by weight. ~ 85% visible light transmittance (JIS K-
6714-1988), which is capable of seeing through the knitting structure of the fiber knitted fabric for the base fabric and has glittering properties. 3. A base fabric made of a fiber woven fabric, and a transparent and colored or colorless thermoplastic resin coating layer on at least one surface of the base fabric, wherein the thermoplastic resin coating layer The outermost layer of a glittering resin containing 0.5 to 10 parts by weight of a pearl pigment with respect to 100 parts by weight of a thermoplastic resin is further formed on the surface of the thermoplastic resin. It has a lightness index L ^* value of 10 to 60 in the CIE 1976 color system defined in 1980, and the pearl pigment has a weight of 70 to
The thermoplastic resin coating layer containing 100% by weight of dichroic interference mica titanium and having the bright resin outermost layer formed thereon has a thickness of 2%.
Visible light transmittance of 5 to 85% (JIS K-6714-
1988), wherein the woven structure of the fiber knitted woven fabric for the base cloth can be seen through and has brilliancy. 4. The transparent or colored, or colored, knitted fabric according to any one of claims 1 to 3, on at least one outermost layer of the transparent composite film material which can be seen through. A glitter composite film material having a colorless thermoplastic resin outermost layer formed thereon and having a transparent woven structure. 5. The fiber knitted and woven fabric for a base fabric, wherein 0 to 40%
Biaxial woven fabric, triaxial woven fabric,
The glitter composite film material according to any one of claims 1 to 4, which is selected from an axial knitted fabric. 6. A brilliant resin coating layer which covers the surface of a base fabric made of a fiber knitted and woven fabric, and which contains 100 parts by weight of a thermoplastic resin and 0.5 to 10 parts by weight of a pearl pigment. And a backside resin coating layer made of a thermoplastic resin, which covers the backside of the base cloth, and the fiber woven fabric for the base cloth is a CIE1976 color system defined in JIS Z-8729-1980. Lightness index L ^* value of 10 to 60,
And a woven tissue porosity of 15 to 40%,
The pearl pigment contains 70 to 100% by weight of the weight of the dichroic interference mica titanium, and the glittering resin coating layer has
Visible light transmittance of 5 to 85% (JIS K-6714-
Have 1988), a possible perspective knitted weave of lightness index L ^* value, and has a bright, lightness index L ^* value of the back resin coating layer, in the range of 10 to 60 Yes,
In addition, the fiber knitted woven fabric for the base cloth has a different lightness index L ^* value, and the lightness index L ^* value difference between the fiber knitted woven fabric for the base cloth and the back surface resin coating layer is 5 to 45, A brilliant composite film material having a woven structure that can be seen through. 7. A brilliant resin coating layer which covers the surface of a base fabric made of a fiber knitted and woven fabric, and which contains 100 parts by weight of a thermoplastic resin and 0.5 to 10 parts by weight of a pearl pigment. And a back surface resin coating layer made of a thermoplastic resin, which covers the back surface of the base fabric, and further, on the surface of the glitter resin coating layer, a glitter resin outermost layer is further formed. The resin outermost layer contains 0.5 to 10 parts by weight of a pearl pigment having a different interference color from the pearl pigment contained in the glittering resin layer with respect to 100 parts by weight of the thermoplastic resin, and The fabric has a CIE1976 color system lightness index L ^* value of 10 to 60 specified in JIS Z-8729-1980 and a woven fabric porosity of 15 to 40%. 70 to 10
The glittering resin coating layer containing 0% by weight of dichroic interference mica titanium and having the glittering resin outermost layer formed thereon has a thickness of 25 to 8
5% visible light transmittance (JIS K-6714-198)
8), which can see through a knitted structure having a lightness index L ^* value, and has brilliancy, and the lightness index L ^* value of the back surface resin coating layer is in the range of 10 to 60. There, and has the lightness index L ^* value different from the base fabric for textile knitted woven fabric, the lightness index L ^* value difference based on the fabric for textile knitted woven fabric with the back resin coating layer, is from 5 to 45 A brilliant composite film material having a woven structure that can be seen through. 8. A base fabric made of a fiber knitted woven fabric, and a transparent and colored or colorless thermoplastic resin coating layer covering a surface of the base fabric and a back surface of the base fabric. And a back surface resin coating layer made of a thermoplastic resin, and having a pearl pigment content of 0.5 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin on the surface of the thermoplastic resin coating layer. The outermost layer of the conductive resin is formed, and the fiber knitted and woven fabric for the base fabric is used as a lightness index L ^* value of 10 to 6 in the CIE1976 color system specified in JIS Z-8729-1980.
0, and a woven fabric porosity of 15 to 40%, and the pearl pigment is 70 to 100% by weight of the weight thereof.
The dichroic interference mica titanium, the thermoplastic resin coating layer on which the glittering resin outermost layer is formed has a visible light transmittance of 25 to 85% (JIS K-6714-1988), The woven fabric having a lightness index L ^* value can be seen through and has glitter, and the lightness index L ^* value of the back surface resin coating layer is in the range of 10 to 60, and the base fabric fiber The knitted fabric has a lightness index L ^* value different from that of the knitted fabric, and the lightness index L ^* value difference between the base fabric fiber knitted fabric and the backside resin coating layer is 5 to 45. A bright composite film material that can be seen through. 9. The transparent or colored, or colored, knitted fabric according to any one of claims 6 to 8, on the outermost layer on at least one surface of the transparent composite film material which can be seen through. A brilliant composite film material having a knitted structure visible therethrough, wherein a colorless thermoplastic resin outermost layer is formed. 10. The fibrous woven fabric for a base fabric, wherein
The glitter composite film according to any one of claims 6 to 9, which is selected from a biaxial knitted fabric, a triaxial knitted fabric, and a four-axis knitted fabric having a woven fabric porosity of 0%. Wood. 11. The fiber knitted and woven fabric for a base fabric according to JIS
CIE197 defined in Z-8729-1980
A混編woven fabric having different two or more kinds of fiber yarns in the lightness index L ^* value of 6 color system, lightness L ^* value of each of the two or more fiber yarns is 10 to 60 A brilliant composite film material capable of seeing through the knitting structure according to any one of claims 1 to 10. 12. The fiber knitted and woven fabric for a base fabric according to JIS
CIE197 defined in Z-8729-1980
6 At least 1 of lightness index L ^{* of} color system of 10 to 60
2. A mixed knitted woven fabric comprising at least one kind of fiber yarn and at least one kind of fiber yarn having a lightness index L ^* value of 61 to 98.
11. A brilliant composite film material capable of seeing through the knitted structure according to any one of items 10 to 10. 13. The fiber woven fabric for a base fabric according to claim 1, wherein the fiber woven fabric comprises at least one selected from carbon fiber multifilament yarn, aramid fiber multifilament yarn, and polyester multifilament fiber yarn. A brilliant composite film material capable of seeing through the knitting structure according to any one of the preceding claims. 14. The fiber woven fabric for a base fabric comprises a multifilament yarn, and the yarn is colored with a pigment or a dye before or after spinning.
14. A brilliant composite film material according to any one of the above items 13, wherein the woven structure can be seen through. 15. The fibrous woven fabric for a base fabric comprises a multifilament yarn, and the yarn is surface-coated with a paint containing a pearl pigment containing 70 to 100% by weight of dichroic interference mica titanium. The glittering composite film material according to any one of claims 1 to 14, wherein the knitting structure can be seen through. 16. The formation of the glitter resin outermost layer is performed by applying and drying a thermoplastic resin solution containing a pearl pigment, or is formed by laminating a thermoplastic resin film containing a pearl pigment. Claim 2, claim 3,
The glitter composite film material according to any one of claims 4, 7, 8, and 9, wherein the woven tissue can be seen through. 17. The method of forming a glittering resin coating layer, which is performed by applying and drying a thermoplastic resin solution containing a pearl pigment, or is formed by laminating a thermoplastic resin film containing a pearl pigment. Claim 1, Claim 4,
The glittering composite film material according to any one of claims 6 and 9, wherein the knitting structure can be seen through. 18. The pearl pigment, comprising 70 to 99% by weight of dichroic interference mica titanium, silver white mica titanium, and / or
Or containing 1 to 30% by weight of chromatic mica iron oxide,
A brilliant composite film material through which the knitted structure according to any one of claims 1 to 17 can be seen. 19. The textile structure according to claim 1, wherein the glittering resin coating layer, the glittering resin outermost layer, or the thermoplastic resin outermost layer is formed with irregularities. Possible glitter composite film material. 20. A color difference ΔE ^* ab (JIS Z-8729) between the fiber woven fabric for base cloth and the glittering resin coating layer, the glittering resin outermost layer, or the thermoplastic resin outermost layer.
-1980) is 6.0 or more, the glitter composite film material according to any one of claims 1 to 19, wherein the woven structure can be seen through.