KR102327838B1 - Laminated film - Google Patents

Abstract

The present specification provides a substrate: a first coating layer formed on the substrate; and a second coating layer formed on the first coating layer, wherein the first coating layer and the second coating layer are each formed from a composition including a silicone-based resin and a curing agent, the silicone-based resin comprising polydimethylsiloxane, When the molar (mol) ratio of Si-vinyl group:Si-CH ₃ group of polydimethylsiloxane is a:b, a/b is greater than 0.015.

Description

Laminated film {LAMINATED FILM}

This specification relates to a laminated film.

Polydimethylsiloxane (PDMS) has high light transmittance and is flexible, so it can be applied to the manufacture of flexible color filters or fluorescent layers. However, since PDMS has a low surface energy and poor adhesion to the same PDMS or other polymers, it was difficult to form a coating layer in a laminated structure. When two or more color filter layers or a combination of color filters and fluorescent layers are required, a PDMS/PDMS laminate structure is required to prevent warping or twisting due to differences in material properties between each coating layer, and a material with excellent interlayer adhesion is selected Needs to be.

Korean Publication No. 10-2013-0078158

The present specification provides a laminated film having excellent adhesion.

An exemplary embodiment of the present specification describes:

a first coating layer formed on the substrate; and

a second coating layer formed on the first coating layer;

The first coating layer and the second coating layer are each formed from a composition comprising a silicone-based resin and a curing agent,

The silicone-based resin includes polydimethylsiloxane,

The polydimethylsiloxane is a Si-vinyl group: Si-CH _{3 When} the molar (mol) ratio of the group is a: b, a/b provides a laminated film that is greater than 0.015.

The laminated film according to an exemplary embodiment of the present specification has excellent adhesion between the first coating layer and the second coating layer, so that interlayer separation does not occur.

1 is a diagram illustrating the structure of a laminated film according to an embodiment of the present specification.
2 is a diagram showing the NMR measurement results of the PDMS subject used in Examples 1 and 2;
3 is a view showing the NMR measurement results of the curing agent in Examples 1 and 2.
4 is a diagram showing NMR measurement results of the PDMS subject used in Comparative Example 1. FIG.
5 is a view showing the NMR measurement results of the curing agent used in Comparative Example 1.
6 is a diagram showing the NMR measurement results of the PDMS subject used in Comparative Example 2.
7 is a view showing the NMR measurement results of the curing agent used in Comparative Example 2.

Hereinafter, the present specification will be described in detail.

In the present specification, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.

In the present specification, when a member is said to be located "on" another member, this includes not only a case in which a member is in contact with another member but also a case in which another member exists between the two members.

An exemplary embodiment of the present specification describes:

a first coating layer formed on the substrate; and

a second coating layer formed on the first coating layer;

The first coating layer and the second coating layer are each formed from a composition comprising a silicone-based resin and a curing agent,

The silicone-based resin includes polydimethylsiloxane,

The polydimethylsiloxane Si-vinyl group: Si-CH _{3 When the} molar ratio of the group content ratio is a: b, a/b provides a laminated film that is greater than 0.015.

In one embodiment of the present specification, the substrate is polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (polyetheretherketone), polyethersulfone (polyethersulfone, PS), polycarbonate (polycarbonate, PC), polypropylene (PP), polyimide (polyimide), acrylic film, and includes at least one of paper. Specifically, the substrate is PET.

In an exemplary embodiment of the present specification, the first coating layer and the second coating layer include a silicone-based resin.

In an exemplary embodiment of the present specification, the silicone-based resin includes polydimethylsiloxane (PDMS).

In one embodiment of the present specification, the first coating layer and the second coating layer each include polydimethylsiloxane.

In an exemplary embodiment of the present specification, the laminated film has a laminate structure of a base material/a first coating layer including polydimethylsiloxane/a second coating layer including polydimethylsiloxane.

An exemplary embodiment of the present specification is that both the first coating layer and the second coating layer contain polydimethylsiloxane satisfying a content ratio between a _{constant Si-vinyl group and a Si-CH 3 group, whereby the adhesive strength between the first coating layer and the second coating layer} this is excellent

In an exemplary embodiment of the present specification, the polydimethylsiloxane is represented by the following formula (1).

[Formula 1]

In Formula 1,

m and n are each an integer from 1 to 10,000.

In an exemplary embodiment of the present specification, a/b is greater than 0.015 when the molar (mol) ratio of the _{Si-vinyl group: Si-CH 3 group of the polydimethylsiloxane is a: b.}

In the exemplary embodiment of the present specification, the upper limit of a/b is not limited, but may be, for example, 0.5.

In an exemplary embodiment of the present specification, when the a/b is greater than 0.015, the adhesion between the first coating layer and the second coating layer is improved.

In the exemplary embodiment of the present specification, the Si-vinyl group means _{, in Formula 1, Si-CH 2} =CH _{2 .}

In an exemplary embodiment of the present specification, the Si-vinyl group of the polydimethylsiloxane participates in the curing reaction.

In one embodiment of the present specification, the Si-vinyl group participates in the curing reaction, thereby improving the durability and peeling force of the coating layer

In an exemplary embodiment of the present specification, the Si-vinyl group of the polydimethylsiloxane: The molar (mol) ratio of the _{Si-CH 3 group is measured using NMR.} Specifically, the polydimethylsiloxane main agent and curing agent applied to the coating layer are _{dissolved in CDCl 3} and confirmed by measuring the H-NMR spectrum with a Burker AVANCEIII 700 MHz NMR instrument.

In an exemplary embodiment of the present specification, in the NMR spectrum, a Si-vinyl group was confirmed as a peak of 5.6 to 6.2, and a Si-CH ₃ group was confirmed as a peak of 0.0 to 0.5.

In an exemplary embodiment of the present specification, the polydimethylsiloxane contains 90 mol% to 98 mol% of _{Si-CH 3 based on the total mol% of functional groups.}

In one embodiment of the present specification, the curing agent is a silicone-based curing agent.

In an exemplary embodiment of the present specification, the silicone-based curing agent may be a hydrogen silane represented by the following formula (2).

[Formula 2]

In Formula 2,

a and b are each an integer from 1 to 500;

In the exemplary embodiment of the present specification, based on 100 parts by weight of the silicone-based resin, the silicone-based curing agent is included in an amount of more than 10 parts by weight and 100 parts by weight or less.

In an exemplary embodiment of the present specification, physical properties such as hardness and tensile strength of the coating layer (PDMS layer) may be controlled by controlling the content of the silicone-based curing agent.

In an exemplary embodiment of the present specification, the first coating layer and the second coating layer are formed from a composition including the silicone-based resin and the curing agent. Specifically, it is formed from a composition comprising the main material of the silicone-based resin and a curing agent. More specifically, the first coating layer and the second coating layer are formed from a composition comprising a base material of polydimethylsiloxane and a curing agent.

In one embodiment of the present specification, the subject means polydimethylsiloxane before curing. The subject has a structure similar to that of Chemical Formula 1, but has a short chain length and is fluid. When heat is applied after mixing with a curing agent, curing occurs through crosslinking with the curing agent.

In one embodiment of the present specification, the first coating layer may be formed by applying the composition on a substrate and then curing.

In the exemplary embodiment of the present specification, the second coating layer may be formed by applying the composition on the first coating layer and then curing.

In an exemplary embodiment of the present specification, the laminated film is cured after applying a first composition on a substrate to form a first coating layer, and applying a second composition on the first coating layer and then curing the second coating layer produced by forming

In one embodiment of the present specification, the first composition and the second composition are the same as the composition described above. For example, the first composition and the second composition each include a silicone-based resin main agent and a curing agent.

In one embodiment of the present specification, the first composition and the second composition are the same as or different from each other.

In one embodiment of the present specification, the first composition and the second composition further include different color conversion materials.

In one embodiment of the present specification, the color conversion material is at least one of a pigment and a phosphor.

In an exemplary embodiment of the present specification, a known method such as bar coating, doctor blading, reverse roll coating or gravure roll coating may be used for the application.

In one embodiment of the present specification, the curing may use heat, ultraviolet rays, electromagnetic rays, and the like. Specifically, thermal curing may be used.

In one embodiment of the present specification, in the case of thermosetting, for example, it may be carried out at a temperature of 80 ℃ to 200 ℃ 1 minute to 30 minutes.

In one embodiment of the present specification, the thickness of the first coating layer is 100 μm to 500 μm.

In one embodiment of the present specification, the thickness of the second coating layer is 100 μm to 500 μm.

In an exemplary embodiment of the present specification, the adhesive force between the first coating layer and the second coating layer is 0.5N/cm or more.

The adhesive force is measured using a texture analyzer using a T-peel test method at a speed of 5 mm/sec between the first coating layer and the second coating layer.

In one embodiment of the present specification, the first coating layer and the second coating layer include different color conversion materials.

In one embodiment of the present specification, the color conversion material is at least one of a pigment and a phosphor.

In one embodiment of the present specification, the first coating layer and the second coating layer include different pigments.

In an exemplary embodiment of the present specification, the pigment may be used alone or mixed with a red pigment, a green pigment, and a yellow pigment as a material (colorant) for expressing a color.

In the present specification, definitions known in the art may be used for the red pigment, green pigment and yellow pigment. For example, a yellow pigment is a pigment expressing a wavelength selected from a wavelength of 500 nm to 780 nm, a green pigment is a pigment light expressing a wavelength selected from a wavelength of 500 nm to 570 nm, and a red pigment is selected from a wavelength of 600 nm to 780 nm It is a pigment that expresses a wavelength.

In the exemplary embodiment of the present specification, the pigment may be included by selecting an appropriate material according to a desired emission color. For example, as the pigment, CIReactive RED-c (c: 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1; 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279), CIReactive Yellow-d (d: 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214) is not limited only.

In an exemplary embodiment of the present specification, the first coating layer and the second coating layer include different phosphors.

In one embodiment of the present specification, the phosphor is a material emitting fluorescence by irradiation with light, radiation, etc., and a yellow phosphor, a green phosphor, and a red phosphor may be used alone or mixed with each other.

In the present specification, definitions known in the art may be used for the yellow phosphor, the green phosphor, and the red phosphor. For example, the yellow phosphor is a phosphor that emits light having a dominant wavelength in the range of 540 nm to 585 nm in response to blue light (430 nm to 480 nm), and the green phosphor is a phosphor that emits light having a dominant wavelength in the range of 600 nm to 650 nm in response to blue light (430 nm to 480 nm) It is a phosphor that emits light having a wavelength. The red phosphor is a phosphor that emits light having a dominant wavelength in the range of 650 nm to 780 nm in response to blue light (430 nm to 480 nm).

In an exemplary embodiment of the present specification, the green phosphor may be a silicate-based, nitride-based or sulfide-based phosphor.

In the exemplary embodiment of the present specification, the red phosphor may be a nitrite-based, sulfide-based or fluorite-based phosphor.

In one embodiment of the present specification, the laminated film is applicable to a polarizing plate, a display device, a carbon fiber prepreg sheet, a flexible printed wiring board, a fluorescent layer or a color filter layer of a vehicle lamp.

Hereinafter, examples will be given to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present specification to those of ordinary skill in the art.

Example 1.

After coating the first composition on the PET substrate, it was dried at 150° C. for 10 minutes to form a first coating layer with a thickness of 100 μm. After the second composition was applied on the first coating layer, it was dried at 150° C. for 10 minutes to form a second coating layer having a thickness of 500 μm.

The first and second compositions were formed by mixing 100 parts by weight of a curing agent with respect to 100 parts by weight of the main agent of PDMS (SR-580, Heesung STS).

Example 2.

After coating the first composition on the PET substrate, it was dried at 150° C. for 10 minutes to form a first coating layer with a thickness of 100 μm. After the second composition was applied on the first coating layer, it was dried at 150° C. for 10 minutes to form a second coating layer having a thickness of 500 μm.

The first composition was formed by mixing 100 parts by weight of a curing agent and 50 parts by weight of a red phosphor with respect to 100 parts by weight of the main agent of PDMS (SR-580, Heesung STS).

Figure 2 shows the NMR measurement results of the PDMS (SR-580, Heesung STS Co., Ltd.) used in Examples 1 and 2 above.

3 shows the NMR measurement results of the curing agent in Examples 1 and 2 above.

The second composition was formed by mixing 100 parts by weight of a curing agent, 0.6 parts by weight of a red pigment, and 0.4 parts by weight of a yellow pigment with respect to 100 parts by weight of the main agent of PDMS (SR-580, Heesung STS).

Comparative Example 1.

After coating the first composition on the PET substrate, it was dried at 150° C. for 10 minutes to form a first coating layer with a thickness of 100 μm. After the second composition was applied on the first coating layer, it was dried at 150° C. for 10 minutes to form a second coating layer having a thickness of 500 μm.

The first composition and the second composition were formed by mixing 10 parts by weight of a curing agent with respect to 100 parts by weight of the main agent of PDMS (sylgard 184, Dow).

Figure 4 shows the NMR measurement results of the PDMS (sylgard 184, Dow company) used in Comparative Example 1.

5 shows the NMR measurement results of the curing agent used in Comparative Example 1.

Comparative Example 2.

After coating the first composition on the PET substrate, it was dried at 150° C. for 10 minutes to form a first coating layer with a thickness of 100 μm. After the second composition was applied on the first coating layer, it was dried at 150° C. for 10 minutes to form a second coating layer having a thickness of 500 μm.

The first composition and the second composition were formed by mixing 10 parts by weight of a curing agent with respect to 100 parts by weight of the main agent of PDMS (KE-106, Shinetsu Corporation).

6 shows the NMR measurement results of the PDMS (sylgard 184, Dow company) subject used in Comparative Example 2.

7 shows the NMR measurement results of the curing agent used in Comparative Example 2.

_{The Si-vinyl group/Si-CH 3} values of the PDMS used in Examples 1 and 2 and Comparative Examples 1 and 2, and the adhesive force between the first coating layer and the second coating layer are shown in Table 1 below.

The Si-vinyl group/Si-CH ₃ value was measured by H-NMR using a Burker AVANCEIII 700 MHz NMR instrument after dissolving PDMS and a curing agent in CDCl 3 .

The adhesion between the first coating layer and the second coating layer was measured using a texture analyzer using a T-peel test method at a speed of 5 mm/sec .

Si-vinyl group/Si-CH ₃ (molar ratio) adhesion Example 1 0.0164 O Example 2 0.0164 0 Comparative Example 1 0.0110 X Comparative Example 2 0.0085 X

In the adhesive force of Table 1, O means that the first coating layer and the second coating layer are not separated, and X means that the adhesive force between the first coating layer and the second coating layer exhibits a value of 0.5 N/cm or less.

10: description
20: first coating layer
30: second coating layer

Claims (7)

write:
a first coating layer formed on the substrate; and
a second coating layer formed on the first coating layer;
The first coating layer and the second coating layer are each formed from a composition comprising a silicone-based resin and a curing agent,
The silicone-based resin includes polydimethylsiloxane,
When the molar (mol) ratio of the Si-vinyl group of the polydimethylsiloxane: Si-CH ₃ group is a: b, a/b is greater than 0.015,
Each of the first coating layer and the second coating layer has a thickness of 100 μm to 500 μm. delete delete The method according to claim 1,
The polydimethylsiloxane is a laminated film comprising 90 mol% to 98 mol% _{of Si-CH 3 groups.} The method according to claim 1,
The curing agent is a laminated film that is a silicone-based curing agent. The method according to claim 1,
The adhesive force between the first coating layer and the second coating layer is 0.5N/cm or more. The method according to claim 1,
The first coating layer and the second coating layer is a laminated film that further comprises a different color conversion material from each other.

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