KR102035717B1 - Laminate and method for manufacturing the same - Google Patents

Abstract

Provided is a technique for preventing cloudiness occurring in a transparent polyimide film. The present invention is a laminate in which a support body and a transparent resin film are laminated so that peeling is possible, wherein the support body has a logarithmic contact angle of a laminated surface with the transparent resin film, A, and also the logarithmic contact angle, B measured after washing the laminated surface with γ-butyrolactone and drying the same, and ¦ B-A ¦ is 8.0 ° or less, and to a production method thereof.

Description

Laminated body and its manufacturing method {LAMINATE AND METHOD FOR MANUFACTURING THE SAME}

TECHNICAL FIELD This invention relates to the laminated body used when manufacturing a laminated body and its manufacturing method, especially the transparent polyimide film with high visibility, and its manufacturing method.

Background Art In recent years, transparent resin films based on polymers such as polyimide and polyamide have been widely used as materials to replace glass that has conventionally been used in accordance with thinning, lightening and flexible display of various image display devices. The cast method (solution casting method) is known as one of the manufacturing methods of such a transparent resin film. In the cast method, generally, varnish containing polymers such as polyimide dissolved in a solvent is applied onto a support to form a film, and after peeling off the supporting substrate, the solvent is removed by drying. Thereby, a resin film can be shape | molded continuously (for example, patent document 1).

In addition, when obtaining a transparent polyimide-type film, although the support body made from metals, such as SUS on the premise of reusability, may be used, the support body which consists of a resin film on the premise of disposables is used from the standpoint of quality control and cost of a support body. In some cases.

Japanese Patent Laid-Open No. 10-310639

When the varnish containing a polyimide-type polymer is apply | coated to a support body, turbidity may generate | occur | produce in the transparent polyimide-type film after peeling from a support body by the influence of the compound which exists in the surface of a support body. When using a resin film as a support body, in order to prevent the wound transfer from a guide roll to a support body, a hard coat layer may be provided, but in that case, in particular, white turbidity tends to arise in the transparent polyimide-type film after peeling. In a film with high transparency, the presence of cloudiness is easy to be visually recognized, and especially in a polyimide type film used for an image display apparatus etc., since cloudiness causes deterioration of visibility and quality deterioration, it must be avoided.

Then, the present inventors discovered the technique which prevents the cloudiness which arises in the above transparent polyimide type film.

That is, this invention is a laminated body by which the support body and the transparent resin film were peelable laminated | stacked, The said support body has the logarithmic contact angle of the laminated surface with the said transparent resin film A, and the said laminated surface is a γ-buty When the logarithmic contact angle measured after washing with Rolactone and drying is set to B, | BA | provides a laminated body characterized by being 8.0 degrees or less.

This invention is also a) apply | coating the resin varnish obtained by mixing and stirring a resin composition for forming a transparent resin film with a solvent on a support body, and the logarithmic contact angle of the laminated surface of the said support body with the said transparent resin film at that time When A and the lamination surface are washed with γ-butyrolactone and dried, the logarithmic contact angle measured after drying is B, and | BA | is 8.0 ° or less; And

b) removing the solvent by drying the applied resin varnish and forming a layer of a transparent resin film on the support;

It provides a method for producing the laminate described above.

The present invention also provides the following aspects:

Said support body is said laminated body whose martens hardness of the side which contacts the said transparent resin film is 300 N / mm <2> or more.

Said laminated body whose said support body is a resin film.

Said laminated body is a resin film which provided the hard-coat layer.

The said laminated body whose said support body is any one of a polyethylene terephthalate film, a cycloolefin type film, an acryl type film, a polyethylene naphthalate film, a polypropylene film, and a triacetyl cellulose film which has a hard-coat layer.

The said laminated body whose said transparent resin film is a polyimide-type film.

Said transparent resin film is 10-500 micrometers of film thickness, The said laminated body which is a polyimide film which has a haze of 1% or less, a total light transmittance of 85% or more, and a yellow index of 4 or less.

Said support body is said laminated body whose arithmetic mean roughness (Ra) prescribed | regulated to JISB0601-2001 of the side which contacts the said transparent resin film is 0.01 micrometer or less.

Said support body is said laminated body whose maximum height (Rz) prescribed | regulated to JISB0601-2001 of the side which contacts the said transparent resin film is 0.1 micrometer or less.

The laminated body film roll which wound up the laminated body of above.

The window film base material obtained by carrying out the solvent drying process of the transparent resin film obtained by peeling from the laminated body as described above further.

A window film comprising a window hard coating layer on at least one surface of the window film substrate described above.

An optical laminated body containing the window film as described above, The optical laminated body which further contains at least 1 layer chosen from the group which consists of a polarizing plate and a touch sensor on one surface of the said window film.

The present inventors discovered that the substance which exists in the surface which the white cloud which generate | occur | produces in a transparent polyimide type film contact | connects the transparent polyimide of a support body is a defect which arises by being transferred to a transparent polyimide type film. Therefore, it was found that the presence of the cause of the turbidity on the support surface can be confirmed by measuring the logarithmic contact angle. That is, the logarithmic contact angle of the laminated surface of the support body with the transparent resin film is first measured and referred to as A, and then the laminated surface is washed with γ-butyrolactone and dried, and then the logarithmic contact angle is measured again as B, When the difference (| BA |) is 8.0 degrees or less, it discovered that the haze hardly generate | occur | produced in a transparent polyimide-type film.

When the difference (| B-A |) of the logarithmic contact angle is 8.0 degrees or less, it means that there is no change in the state of a surface by washing | cleaning with (gamma) -butyrolactone. On the contrary, when | B-A | exceeds 8.0 °, it can be seen that some substance which is soluble in γ-butyrolactone exists on the surface of the support, which causes cloudiness. In the present invention, any material present on the surface of the support can prevent the clouding of the transparent polyimide-based film only by measuring the logarithmic contact angle before and after washing with γ-butyrolactone. It is the operation which can be judged easily, and its usefulness is high, and the big improvement of the yield of manufacture can be considered.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows typically the cross section of the laminated body of this invention.
It is a schematic diagram which shows the coating process of a transparent resin film.
3 is a photograph showing a state where the wound on the roll surface is transferred to a transparent resin film.
4 is a photograph showing a state in which cloudiness exists in the transparent resin film.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows typically the laminated body of this invention, 1 shows a support body, 2 shows a transparent resin film, and 3 is a protective film formed as needed. The transparent resin film 2 is coated by the coating process 12 of the transparent resin film shown in FIG. The support roll 10 shown in FIG. 2 is a roll which wound the support body, and is sent to the coating process 12 through the guide roll 11. Although only one guide roll is described in FIG. 2, it is actually sent to the coating process 12 via several guide rolls. In each guide roll, a certain process is performed or tension is given. In the coating process 12, the varnish of a transparent resin film is coated on the support body 1. After the transparent resin film is coated, it is dried in the predrying step 13. In the predrying step 13, the transparent resin film 2 is dried to maintain the film shape in order to peel the transparent resin film 2 from the support. When the transparent resin film actually used in an image display device or the like is obtained, Although the main drying process which suppresses shrinkage | contraction of the width direction of a transparent resin film with a transverse stretching machine, or extends | stretches while extending | stretching in the width direction is needed, the process is not described in FIG. The protective film 3 unwound from the protective film roll 14 is formed in the surface opposite to the support body 1 of the pre-dried transparent resin film 2, and the three-layer winding roll 15 is formed. do. The support layer 1 and the protective film 3 are peeled off by this three-layer winding roll 15 in another process, and only the transparent resin film 2 is used, and the transparent resin film from which the solvent was fully removed over this drying process is used. Manufacture.

Support

As shown in FIG. 1, the laminated body of this invention consists of a support body 1 and the transparent resin film 2 formed on the support body. As described above, when the logarithmic contact angle of the laminated surface with the transparent resin film is washed with γ-butyrolactone and A is the logarithmic contact angle of the laminated surface with the transparent resin film as described above, the logarithmic contact angle measured after drying is B, It is necessary that | BA | be less than or equal to 8.0 °. When the logarithmic contact angles A and B are controlled as described above, clouding of the transparent resin film is prevented. The difference between the logarithmic contact angles before and after washing the support surface with γ-butyrolactone, that is, the value of | BA |, is preferably 0 to 3.5 °, more preferably 0 to 3.0 °, still more preferably 0 to 2.0 °. Especially preferably, it is 0-1.0 degree. When the value of | B-A | is larger than 8.0 °, turbidity often occurs on the surface of the transparent film.

Here, "cloudy" means the cloudiness of the level which can be visually recognized when observing the transparent resin film obtained after peeling from a support body with the high-brightness lamp of 3,000 lumens or more, The measuring method is the film after peeling from a support body, After wash | cleaning a part of surface of a support body with the waste for clean rooms, it can confirm by visually evaluating the external appearance (cloudiness) of the film according to the evaluation criteria of the cloudiness described in the Example using the high brightness light of 3,000 lumens or more of luminous flux.

When the resin varnish is applied to the support, the logarithmic contact angle of the surface of the support (the side on which the resin varnish is applied) is preferably 50 to 120 °, more preferably 60 to 110 °, further preferably 70 to 100 °. to be. If the logarithmic contact angle of the support surface exists in the said range, the edge part of the apply | coated resin varnish does not spread thinly, and since the oscillation of a film piece increases from the edge part of the resin film after peeling from a support body, it becomes hard to become a cause of process contamination In addition, the contact angle of the surface of the resin film obtained by peeling from the support also tends to be less likely to increase, and there is a concern that problems such as poor coating may occur when the resin film is subjected to surface treatment such as hard coating coating in a later step. Less

In order to evaluate the hydrophilicity (or hydrophobicity) of the surface of an object, the logarithmic contact angle is to measure the angle at which the water droplet is in contact with the surface by dropping the droplet on the surface of the object. (DM500) using ultrapure water by the θ / 2 method. More detailed measuring methods are described in the Examples. Moreover, logarithmic contact angle B is wash | cleaned with the clean room waste which infiltrated (gamma) -butyrolactone after a predetermined time after dripping (gamma) -butyrolactone on the laminated surface side surface with the transparent resin film of a support body, and further surface After the remaining γ-butyrolactone is dried, water is added dropwise to measure the logarithmic contact angle in a similar manner, and the hydrophilicity (or hydrophobicity) after washing the surface with γ-butyrolactone is evaluated. The more detailed measuring method of this logarithmic contact angle B is also described in an Example. In order to reduce the influence of a measurement error, a logarithmic contact angle is measured 10 times or more, and the average value is made into A or B.

As for the support body 1, it is preferable that the Martens hardness of the side which contacts the transparent resin film 2 is 300 N / mm <2> or more.

Martens hardness was obtained by bonding a sample of a predetermined size to glass using an ultra-micro hardness tester (FISCHERSCOPE HM2000: manufactured by Fischer Instruments) in an atmosphere of 23 ° C and 55% RH. , The value was measured by holding for 5 seconds while maintaining the load of 0.5 mN after applying the load at a pressure of 0.5 mN / 5 seconds. The detailed measuring method of martens hardness is described in an Example.

In the present invention, the Martens hardness is preferably 300 N / mm 2 or more, more preferably 350 N / mm 2 or more, still more preferably 380 N / mm 2 or more, particularly preferably 400 N / mm 2 or more. The upper limit of the Martens hardness is not particularly limited, but in the case of a support having a hard coating layer, if the martens hardness is too high, the hard coating layer may break during transportation, and usually 700 N / mm 2 or less, preferably 650 N / mm 2. Hereinafter, More preferably, it is 600 N / mm <2> or less. When the Martens hardness of the side in contact with the transparent film of the support is 300 N / mm 2 or more, the wound present on the roll such as the guide roll is transferred onto the support, and the wound is transferred to the transparent resin film formed thereafter. It becomes hard to occur. An example thereof is shown in FIG. 3. In this specification, the wound of a transparent resin film means the case where the presence of a wound is confirmed by visually confirming the presence or absence of a wound by irradiating the high brightness lamp of 3,000 lumens or more for the transparent resin film peeled from the support body. Usually, in the film for optical use, the appearance quality of a wound etc. is often evaluated under fluorescent lamps, but when it is used as a visual side of an image display apparatus, especially a front plate (window film), the required level of appearance quality is high, It is also necessary to suppress the wound which cannot be recognized under fluorescent lamps. If it is a high-brightness lamp of 3,000 lumens or more, not only the wound visually recognized under fluorescent lamps, but also the presence or absence of the wound which is weak more visibility can be evaluated.

In this invention, what is necessary is just to limit the logarithmic contact angle of the surface of the one side of a support body, ie, the side which contacts a transparent resin film to the said range, and does not depend in particular on the material of a support body. The support body may be a metal belt such as stainless steel, or may be a resin film. In the case of the resin film, in order to satisfy | fill the value of the said contact-angle difference (| B-A |), what provided the hard coat layer in the one side may be sufficient. Preferable supports include polyethylene terephthalate (PET) film, cycloolefin-based film (COP), acrylic film, polyethylene naphthalate film, polypropylene film, and a hard coating layer formed on one side of a triacetyl cellulose film. As a more preferable support body, the thing which provided the hard coat layer in the PET film and the one side of a cycloolefin type film, and the most preferable support body form the hard coat layer in the one side of PET film. Although a hard coating layer is not specifically limited, Any of an acryl type, a urethane type, and an epoxy type may be sufficient.

When using what provided the hard coat layer in the one side of a resin film as a support body, it can form by the method of apply | coating the hard coating composition to one side of a resin film, and hardening. As a composition for hard coating, the composition which contains a photocurable (meth) acrylate monomer, an oligomer, and a polymerization initiator, and contains a solvent normally is mentioned, for example. As a polymerization initiator, a photoinitiator is used normally and hardening is performed by irradiating an ultraviolet-ray.

In the case of using a hard coat layer formed on one side of the resin film as the support, the logarithmic contact angle difference can be adjusted by the curing conditions at the time of forming the hard coat layer. For example, the hard coat layer is formed while purging with nitrogen during UV curing. Alternatively, when a large amount of polymerization initiator is added as a composition for forming the hard coat layer, the logarithmic contact angle difference can be reduced. Moreover, it can also adjust by washing | cleaning after forming a hard-coat layer, and a logarithmic contact angle difference can be made small by washing with an organic solvent after forming a hard-coat layer.

It is preferable that the arithmetic mean roughness Ra of the surface (side in contact with a transparent resin film) of the support body of this invention is a predetermined range. Arithmetic mean roughness Ra is measured using a contact roughness meter and complies with JIS B0601-2001. Arithmetic mean roughness Ra of the surface of a support body becomes like this. Preferably it is 0.01 micrometer or less, More preferably, it is 0.008 micrometer or less, More preferably, it is 0.006 micrometer or less. Since the shape of the side contacting the transparent resin film, that is, the surface, is transferred to the surface of the transparent resin film, the smaller the arithmetic mean roughness Ra of the surface of the support, the easier the glossiness of the transparent resin film is obtained, and the image It is suitable for the case where it arrange | positions in a display apparatus. The lower limit of the arithmetic mean roughness Ra of the surface of the support is not particularly limited, but the smaller the better.

It is preferable that the maximum height Rz of the surface of the support body of this invention is a predetermined range. The maximum height Rz is measured using a contact illuminometer and complies with JIS B0601-2001. The maximum height Rz of the surface of the support is preferably 0.1 µm or less, more preferably 0.08 µm or less, and still more preferably 0.05 µm or less. Since the shape of the side contacting the transparent resin film, that is, the surface, is transferred to the surface of the transparent resin film, when the maximum height Rz of the surface of the support is large, the local uneven height of the surface of the transparent resin film also becomes large. It tends to be a rough surface. Therefore, the smaller the maximum height Rz of the surface of the support, the better. Especially, it is suitable for the case where it arrange | positions in an image display apparatus. The lower limit of the maximum height Rz of the surface of the support is not particularly limited, but smaller is better.

The support body useful for this invention can be used also as a commercial item. For example, the hard coating film marketed by Toray Co., Ltd. under the name of a tough top (trademark), the hard coating film marketed by Kimoto Co., Ltd. under the name of a KB film (trademark), and Toyocross The hard coat film etc. marketed by the name of Toklo (trademark) HC film from Co., Ltd. are mentioned. Of course, as long as the requirements of the logarithmic contact angle are satisfied, another film may be used, and it is not necessary to be a hard coat film.

Transparent resin film

The transparent resin film which comprises the laminated body of this invention consists of a resin composition containing at least 1 sort (s) chosen from the group which consists of polyimide, polyamide, and polyamideimide.

In this specification, a polyimide represents the polymer containing the repeating structural unit containing an imide group, and polyamideimide contains both the repeating structural unit containing an imide group, and the repeating structural unit containing an amide group. A polymer is shown and polyamide shows the polymer containing the repeating structural unit containing an amide group. The polyimide polymer refers to a polymer containing any one or more selected from polyimide and polyamideimide.

The polyimide type polymer which concerns on this embodiment has a repeating structural unit represented by Formula (10). Here, G represents a tetravalent organic group and A represents a divalent organic group. G and / or A may include the repeating structural unit represented by two or more types of different formulas (10). In addition, the polyimide polymer which concerns on this embodiment is a repeating structural unit represented by any of Formula (11), Formula (12), and Formula (13) in the range which does not impair the various physical properties of the obtained transparent resin film. One or more of may be included.

If the main structural unit of a polyimide polymer is a repeating structural unit represented by Formula (10), it is preferable from a viewpoint of the intensity | strength and transparency of a transparent resin film. In the polyimide-based polymer according to the present embodiment, the repeating structural unit represented by the formula (10) is preferably 40 mol% or more, more preferably 50 to the total repeating structural units of the polyimide-based polymer. It is at least mol%, more preferably at least 70 mol%, particularly preferably at least 90 mol%, even more preferably at least 98 mol%. 100 mol% may be sufficient as the repeating structural unit represented by Formula (10).

[Formula 1]

G and G ¹ each independently represent a tetravalent organic group, and preferably a tetravalent organic group having 4 to 40 carbon atoms. The said organic group may be substituted by the hydrocarbon group or the fluorine-substituted hydrocarbon group, and in that case, carbon number of a hydrocarbon group and a fluorine-substituted hydrocarbon group becomes like this. Preferably it is 1-8. Examples G and G ^1, formula 20, formula 21, formula 22, formula 23, formula 24, formula 25, formula 26, formula 27, formula 28 Or the group represented by Formula (29) and a trivalent C6 or less chain hydrocarbon group are illustrated. In the formula, * represents a bond, Z represents a single bond, -O-, -CH _2- , -CH ₂ -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) ₂ -,- C (CF ₃ ) _2- , -Ar-, -SO _2- , -CO-, -O-Ar-O-, -Ar-O-Ar-, -Ar-CH ₂ -Ar-, -Ar-C (CH ₃ ) ₂ -Ar- or -Ar-SO ₂ -Ar-. Ar represents the C6-C20 arylene group which may be substituted by the fluorine atom, and a phenylene group is mentioned as a specific example. In an easy to suppress the yellowness index of the transparent resin film obtained point, as the G and G ^1, and preferably formula (20), Equation 21, Equation 22, Equation 23, Equation 24, Equation ( 25), group represented by Formula (26) or Formula (27) is mentioned.

[Formula 2]

G ² represents a trivalent organic group, and preferably a trivalent organic group having 4 to 40 carbon atoms. The said organic group may be substituted by the hydrocarbon group or the fluorine-substituted hydrocarbon group, and in that case, carbon number of a hydrocarbon group and a fluorine-substituted hydrocarbon group becomes like this. Preferably it is 1-8. Examples of G ² include formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), formula (28) or formula Examples of the group in which one of the bonds of the group represented by (29) are substituted with a hydrogen atom and a trivalent C 6 or less chain hydrocarbon group are exemplified. The example of Z in a formula is the same as the example of Z in the description about G.

G ³ represents a divalent organic group, and preferably a divalent organic group having 4 to 40 carbon atoms. The said organic group may be substituted by the hydrocarbon group or the fluorine-substituted hydrocarbon group, and in that case, carbon number of a hydrocarbon group and a fluorine-substituted hydrocarbon group becomes like this. Preferably it is 1-8. Examples of G ^3, formula 20, formula 21, formula 22, formula 23, formula 24, formula 25, formula 26, formula 27, formula 28 or formula Among the bonds of the group represented by (29), a group in which two non-adjacent groups are substituted with a hydrogen atom and a divalent chain hydrocarbon group having 6 or less carbon atoms are exemplified. The example of Z in a formula is the same as the example of Z in the technique regarding G.

A, A ¹ , A ² and A ³ all represent a divalent organic group, and preferably a divalent organic group having 4 to 40 carbon atoms. The said organic group may be substituted by the hydrocarbon group or the fluorine-substituted C1-C8 hydrocarbon group, In that case, carbon number of a hydrocarbon group and a fluorine-substituted hydrocarbon group becomes like this. Preferably it is 1-8. As A, A ¹ , A ^2, and A ³ , formulas (30), (31), (32), (33), (34), (35), (36) and ( 37) or a group represented by formula (38); Groups in which these are substituted by at least one of methyl group, fluoro group, chloro group or trifluoromethyl group; And a chain hydrocarbon group having 6 or less carbon atoms.

In the formula, * represents a bond, and Z ¹ , Z ² and Z ³ each independently represent a single bond, -O-, -CH _2- , -CH ₂ -CH _2- , -CH (CH ₃ )- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -S-, -SO _2- , -CO- or -NR ² . Here, R <^2> represents the C1-C12 hydrocarbon group which may be substituted by the halogen atom. Here, R <^2> represents the C1-C12 hydrocarbon group which may be substituted by the halogen atom. It is preferable that Z <^1> and Z <^2> and Z <^2> and Z <^3> are located in a meta position or a para position with respect to each ring, respectively.

[Formula 3]

In this invention, the resin composition which forms a transparent resin film may contain polyamide. The polyamide which concerns on this embodiment is a polymer which mainly uses the repeating structural unit represented by Formula (13). Preferred examples and specific examples of G ³ and A ^{3 in} the polyamide are the same as those of the preferred examples and specific examples of G ³ and A ^{3 in} the polyimide polymer. The said polyamide may contain the repeating structural unit represented by two or more types of formula (13) from which G <^3> and / or A <^3> differ.

The polyimide polymer can be obtained, for example, by polycondensation of a diamine and a tetracarboxylic acid compound (tetracarboxylic dianhydride, etc.), for example, JP-A-2006-199945 or JP-A It can synthesize | combine according to the method described in Unexamined-Japanese-Patent No. 2008-163107. As a commercial item of a polyimide, the Mitsubishi Gas Chemical Co., Ltd. neoprem (registered trademark), Kawamura Industrial Co., Ltd. KPI-MX300F, etc. are mentioned.

As a tetracarboxylic acid compound used for the synthesis | combination of a polyimide type polymer, Aromatic tetracarboxylic acid and its anhydride, Preferably aromatic tetracarboxylic acid compounds, such as the dianhydride; And aliphatic tetracarboxylic acid compounds such as aliphatic tetracarboxylic acids and anhydrides thereof, and preferably dianhydrides thereof. The tetracarboxylic acid compound may be a tetracarboxylic acid compound derivative such as a tetracarboxylic acid chloride compound in addition to the anhydride, and these may be used alone or in combination of two or more thereof.

Specific examples of the aromatic tetracarboxylic dianhydride include non-condensed polycyclic aromatic tetracarboxylic dianhydrides, monocyclic aromatic tetracarboxylic dianhydrides and condensed polycyclic aromatic tetracarboxylic dianhydrides. As a non-condensed polycyclic aromatic tetracarboxylic dianhydride, 4,4'- oxydiphthalic dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 2,2', 3,3 '-Benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3' , 4,4'-diphenylsulfontetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride , 2,2-bis (3,4-dicarboxyphenoxyphenyl) propane dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride (may be described as 6FDA), 1, 2-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,2-bis (3,4-dicarboxyphenyl) ethane dianhydride Water, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, non (2,3-dicarboxyphenyl) methane dianhydride, 4,4 '-(p-phenylenedioxy) diphthalic dianhydride, and 4,4'-(m-phenylenedioxy) diphthalic dianhydride are mentioned. . As monocyclic aromatic tetracarboxylic dianhydride, 1,2,4,5-benzenetetracarboxylic dianhydride is used. As condensed polycyclic aromatic tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid Main dianhydrides are mentioned.

Among these, 4,4'- oxydiphthalic dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 2,2', 3,3'- benzophenone tetracarboxylic acid Dianhydrides, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-di Phenylsulfontetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis ( 3,4-dicarboxyphenoxyphenyl) propane dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA), 1,2-bis (2,3-dicarboxyphenyl) ethane Dianhydrides, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydrides, 1,2-bis (3,4-dicarboxyphenyl) ethane dianhydrides, 1,1-bis (3,4-di Carboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, 4,4 '-(p-phenylenediox ) Diphthalic dianhydride and 4,4 '-(m-phenylenedioxy) diphthalic dianhydride, More preferably, 4,4'- oxydiphthalic dianhydride, 3,3', 4,4 '-Biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA), bis (3,4-dicarboxyphenyl) methane dianhydride and 4,4 '-(p-phenylenedioxy) diphthalic dianhydride are mentioned. These can be used individually or in combination of 2 or more types.

As aliphatic tetracarboxylic dianhydride, a cyclic or acyclic aliphatic tetracarboxylic dianhydride is mentioned. A cyclic aliphatic tetracarboxylic dianhydride is tetracarboxylic dianhydride which has an alicyclic hydrocarbon structure, As a specific example, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 1,2,3,4- Cycloalkanetetracarboxylic dianhydrides such as cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3, 5,6-tetracarboxylic dianhydride, dicyclohexyl 3,3'-4,4'-tetracarboxylic dianhydride, and positional isomers thereof. These can be used individually or in combination of 2 or more types. Specific examples of the acyclic aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and the like. It can use combining a species or more. Moreover, you may use combining cyclic aliphatic tetracarboxylic dianhydride and acyclic aliphatic tetracarboxylic dianhydride.

Among the tetracarboxylic acid compounds, the alicyclic tetracarboxylic dianhydride or the non-condensed polycyclic aromatic tetracarboxylic dianhydride is preferably used from the viewpoint of easily improving the elastic modulus, the flex resistance and the optical properties of the transparent resin film. have. As a more preferable specific example, 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride, 2,2', 3,3'-biphenyl tetracarboxylic dianhydride, 2,2-bis (3,4 -Dicarboxyphenyl) propane dianhydride and 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA). These can be used individually or in combination of 2 or more types.

In addition to the anhydride of tetracarboxylic acid used for said polyimide synthesis, the polyimide type polymer which concerns on this embodiment is a tetracarboxylic acid and a tricarboxylic acid compound in the range which does not impair the various physical properties of the obtained transparent resin film. And dicarboxylic acid compounds, anhydrides thereof and derivatives thereof may be further reacted.

As a tricarboxylic acid compound, aromatic tricarboxylic acid, aliphatic tricarboxylic acid, these lead acid chloride compounds, an acid anhydride, etc. are mentioned, These may use 2 or more types together. Specific examples thereof include anhydrides of 1,2,4-benzenetricarboxylic acid; 2,3,6-naphthalenetricarboxylic acid-2,3- anhydride; Phthalic anhydride and benzoic acid single _{bond, -CH 2 -, -C (CH} 3) 2 -, -C (CF 3) 2 -, -SO 2 - or can be connected to the compound group-phenylene.

As a dicarboxylic acid compound, aromatic dicarboxylic acid, aliphatic dicarboxylic acid, those flexible acid chloride compounds, an acid anhydride, etc. are mentioned, These may use 2 or more types together. Specific examples thereof include terephthalic acid; Isophthalic acid; Naphthalene dicarboxylic acid; 4,4'-biphenyldicarboxylic acid; 3,3'-biphenyldicarboxylic acid; Of chain hydrocarbons having 8 or less carbon atoms. The dicarboxylic acid compound and the two benzoic acid backbones are -CH _2- , -S-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -O-, -NR ^9- , -C (= And compounds linked with an O)-, -SO ₂ -or a phenylene group. These can be used individually or in combination of 2 or more types. Here, R <^9> represents the C1-C12 hydrocarbon group which may be substituted by the halogen atom.

As a dicarboxylic acid compound, Preferably, it is terephthalic acid; Isophthalic acid; 4,4'-biphenyldicarboxylic acid; 3,3'-biphenyldicarboxylic acid; And a compound in which two benzoic acid skeletons are linked by a —CH ₂ —, —C (═O) —, —O—, —NR ⁹ —, —SO ₂ —, or a phenylene group, more preferably terephthalic acid; 4,4'-biphenyldicarboxylic acid; And two benzoic acid backbones linked by —O—, —NR ⁹ —, —C (═O) — or —SO ₂ —. These can be used individually or in combination of 2 or more types.

The ratio of the tetracarboxylic acid compound to the total of the tetracarboxylic acid compound, the tricarboxylic acid compound and the dicarboxylic acid compound is preferably 40 mol% or more, more preferably 50 mol% or more, and even more preferably It is 70 mol% or more, More preferably, it is 90 mol% or more, Especially preferably, it is 98 mol% or more.

Aliphatic diamine, aromatic diamine, or mixtures thereof are mentioned as a diamine used for the synthesis | combination of a polyimide type polymer. In addition, in this embodiment, "aromatic diamine" represents the diamine which the amino group couple | bonded with the aromatic ring directly, and may contain the aliphatic group or another substituent in a part of the structure. The aromatic ring may be monocyclic or condensed, and examples thereof include, but are not limited to, a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring and the like. Among these, Preferably a benzene ring is mentioned. Moreover, "aliphatic diamine" shows the diamine which the amino group couple | bonded with the aliphatic group directly, and may contain the aromatic ring and other substituent in a part of the structure.

Specific examples of aliphatic diamines include acyclic aliphatic diamines such as hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, norbornanediamine, 4,4'- Cyclic aliphatic diamines, such as diamino dicyclohexyl methane, etc. are mentioned, These can be used individually or in combination of 2 or more types.

Specific examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, m-xylylenediamine, p-xylylenediamine, 1,5-diaminonaphthalene, 2,6 Aromatic diamine having one aromatic ring, such as -diaminonaphthalene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3 , 4'-diaminodiphenylether, 3,3'-diaminodiphenylether, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diamino Diphenylsulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4 -(3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl (may be referred to as TFMB), 4,4'-bis (4-ami Nophenoxy) biphenyl, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl) fluorene, 9,9-bis (4-amino-3- And aromatic diamines having two or more aromatic rings, such as chlorophenyl) fluorene and 9,9-bis (4-amino-3-fluorophenyl) fluorene. These can be used individually or in combination of 2 or more types.

As aromatic diamine, Preferably, 4,4'- diamino diphenylmethane, 4,4'- diamino diphenyl propane, 4,4'- diamino diphenyl ether, 3,3'- diamino diphenyl ether , 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 1,4-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] Sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy ) Phenyl] propane, 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl (TFMB), 4,4'-bis (4-aminophenoxy C) biphenyl, more preferably 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylether, 4,4'-diamino Diphenylsulfone, 1,4-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] Propane, 2,2'-dimethylbenzidine, 2,2'- (Trifluoromethyl) scan is 4,4'-diaminodiphenyl (TFMB), 4,4'- bis (4-aminophenoxy) biphenyl. These can be used individually or in combination of 2 or more types.

The said diamine may have a fluorine-type substituent. As a fluorine-type substituent, a C1-C5 perfluoroalkyl group, such as a trifluoromethyl group, and a fluoro group are mentioned.

Among the diamines, from the viewpoint of high transparency and low colorability, it is preferable to use one or more selected from the group consisting of aromatic diamines having a biphenyl structure, and as specific examples, 2,2'-dimethylbenzidine, 2,2'- Preference is given to using at least one member selected from the group consisting of bis (trifluoromethyl) -4,4'-diaminodiphenyl (TFMB) and 4,4'-bis (4-aminophenoxy) biphenyl. . It is more preferable that it is a diamine which has a biphenyl structure and a fluorine-type substituent, and it is more preferable to use 2,2'-bis (trifluoromethyl) -4,4'- diamino diphenyl (TFMB) as a specific example.

The polyimide-based polymer is a repeating structure represented by formula (10), which is formed by polycondensation of a diamine and a tetracarboxylic acid compound (including tetracarboxylic acid compound derivatives such as an acid chloride compound and a tetracarboxylic dianhydride). It is a condensation type polymer containing a unit. As starting materials, in addition to these, it further includes tricarboxylic acid compounds (including tricarboxylic acid compound derivatives such as acid chloride compounds and tricarboxylic acid anhydrides) and dicarboxylic acid compounds (derivatives such as acid chloride compounds). May be used). Moreover, polyamide is a condensation type polymer containing the repeating structural unit represented by Formula (13) formed by polycondensation of a diamine and a dicarboxylic acid compound (including derivatives, such as an acid chloride compound).

The repeating structural units represented by the formulas (10) and (11) are usually derived from diamines and tetracarboxylic acid compounds. The repeating structural unit represented by formula (12) is usually derived from a diamine and a tricarboxylic acid compound. The repeating structural unit represented by formula (13) is usually derived from a diamine and a dicarboxylic acid compound. Specific examples of the diamine, tetracarboxylic acid compound, tricarboxylic acid compound, and dicarboxylic acid compound are as described above.

The molar ratio of the diamine and carboxylic acid compounds such as the tetracarboxylic acid compound is preferably suitably adjusted in the range of 0.9 mol or more and 1.1 mol or less with respect to 1.00 mol of diamine. In order to express high corrosion resistance, since it is preferable that the polyimide polymer obtained is high molecular weight, it is more preferable that they are 0.98 mol or more and 1.02 mol of tetracarboxylic acid with respect to 1.00 mol of diamine, and 0.99 mol or more and 1.01 mol It is more preferable that it is below.

Moreover, it is preferable that the ratio of the amino group to the obtained polymer terminal is low from a viewpoint of suppressing the yellowness of the obtained transparent resin film, and it is preferable that carboxylic acid compounds, such as a tetracarboxylic acid compound, are 1.00 mol or more with respect to 1.00 mol of diamines. .

The amount of fluorine in the polyimide polymer obtained by adjusting the fluorine number in the molecule of the diamine and the carboxylic acid compound (for example, the tetracarboxylic acid compound) is 1% by mass or more based on the mass of the polyimide polymer, It can be 5 mass% or more, 10 mass% or more, and 20 mass% or more. The higher the proportion of fluorine, the higher the raw material cost, and therefore, the upper limit of the amount of fluorine is preferably 40% by mass or less. A fluorine-type substituent may exist in any of diamine or a carboxylic acid compound, and may exist in both. In particular, the YI value may be reduced by including a fluorine-based substituent.

The polyimide-based polymer according to the present embodiment may be a copolymer containing a plurality of different kinds of repeating structural units. The weight average molecular weight of standard polystyrene conversion of a polyimide type polymer is 100,000-800,000 normally. When the weight average molecular weight of a polyimide type polymer is large, the flexibility at the time of film-forming improves, Preferably it is 200,000 or more, More preferably, it is 300,000 or more, More preferably, it is 350,000 or more. Moreover, since the varnish of a suitable density | concentration and a viscosity is obtained and there exists a tendency for film-forming property to improve, Preferably it is 750,000 or less, More preferably, it is 600,000 or less, More preferably, it is 500,000 or less. You may use combining two or more types of polyimide polymers of different weight average molecular weights. In addition, you may mix another polymeric material in the range which does not impair physical property.

By including a fluorine-containing substituent, the polyimide polymer and the polyamide exhibit a tendency to decrease the YI value while improving the elastic modulus when forming a film. When the elasticity modulus of a film is high, there exists a tendency for generation | occurrence | production of a wound, a wrinkle, etc. to be suppressed. From the viewpoint of transparency of the film, the polyimide polymer and the polyamide preferably have a fluorine-containing substituent. As a specific example of a fluorine-containing substituent, a fluoro group and a trifluoromethyl group are mentioned.

The content of the fluorine atom in the mixture of the polyimide polymer, the polyimide polymer and the polyamide is based on the sum of the mass of the polyimide polymer or the mass of the polyimide polymer and the mass of the polyamide, respectively. Preferably they are 1 mass% or more and 40 mass% or less, More preferably, they are 5 mass% or more and 40 mass% or less. When content of a fluorine atom is 1 mass% or more, there exists a tendency which can reduce more YI value at the time of film-forming, and can improve transparency more. On the other hand, when the content of the fluorine atom is less than 1% by mass, irregular film formation and the like easily occur during handling due to the generation of static electricity when the film is formed. When content of a fluorine atom is 40 mass% or less, there exists a tendency for the high molecular weight of polyimide to become easy.

In this invention, content of the polyimide type polymer and / or polyamide in the resin composition which comprises a transparent resin film becomes like this. Preferably it is 40 mass% or more with respect to solid content of a resin composition, More preferably, it is 50 mass % Or more, More preferably, it is 60 mass% or more, More preferably, it is 70 mass% or more, and 100 mass% may be sufficient. Flexibility of a transparent resin film is favorable as content of a polyimide polymer and / or a polyamide is more than the said lower limit. In addition, solid content means the total amount of the component remove | excluding the solvent from the resin composition.

In this invention, the resin composition which forms a transparent resin film may further contain inorganic materials, such as an inorganic particle, in addition to the said polyimide polymer and / or polyamide. Examples of the inorganic material include inorganic particles such as silica particles, titanium particles, aluminum hydroxide, zirconia particles, barium titanate particles, and silicon compounds such as quaternary alkoxysilanes such as tetraethyl orthosilicate. From the viewpoint of the stability of the varnish and the dispersibility of the inorganic material, preferably silica particles, aluminum hydroxide, zirconia particles, and more preferably silica particles.

The average primary particle diameter of the inorganic material particles is preferably 1 to 200 nm, more preferably 3 to 100 nm, still more preferably 5 to 50 nm, still more preferably 5 to 30 nm. Transparency tends to improve that the average primary particle diameter of inorganic material particles, such as a silica particle, is 100 nm or less. When the average primary particle diameter of the silica particles is 10 nm or more, the cohesive force of the silica particles is weakened, so that it tends to be easy to handle.

In the present invention, the silica particles may be a silica sol obtained by dispersing the silica particles in an organic solvent or the like, or a silica fine particle powder produced by a gas phase method may be used.

The average primary particle diameter of the silica particle in a transparent resin film can be calculated | required by observation with a transmission electron microscope (TEM). The particle size distribution of the silica particle before forming a transparent resin film can be calculated | required with a commercially available laser diffraction type particle size distribution meter.

In this invention, content of the inorganic material in a resin composition becomes like this. Preferably it is 0 mass% or more and 90 mass% or less with respect to solid content of a resin composition, More preferably, it is 0 mass% or more and 60 mass% or less, More preferably, It is 0 mass% or more and 40 mass% or less. When content of the inorganic material in a resin composition exists in said range, there exists a tendency which is easy to make transparency and mechanical strength of a transparent resin film compatible. In addition, solid content means the total amount of the component remove | excluding the solvent from the resin composition.

The resin composition which comprises a transparent resin film may further contain another component in addition to the component demonstrated above. As another component, antioxidant, a mold release agent, a light stabilizer, a bluing agent, a flame retardant, a lubricating agent, and a leveling agent are mentioned, for example.

In the present invention, when the resin composition contains a resin component such as a polyimide polymer and other components other than the inorganic material, the content of the other components is preferably 0% by mass or more based on the total mass of the transparent resin film. 20 mass% or less, More preferably, they are 0 mass% or more and 10 mass% or less.

In the present invention, the transparent resin film is, for example, a reaction liquid of a polyimide-based polymer and / or polyamide obtained by selecting and reacting from the tetracarboxylic acid compound, the diamine, and the other raw materials, if necessary. It can manufacture with the resin varnish prepared by adding, mixing, and stirring a solvent to the resin composition containing an inorganic material and other components. In the said resin composition, instead of reaction liquids, such as a polyimide polymer, you may use solutions, such as the purchased polyimide polymer, and solutions, such as the purchased polyimide polymer.

As a solvent which can be used for preparing a resin varnish, the organic solvent which can melt | dissolve or disperse resin components, such as a polyimide type polymer, can be selected suitably. From the standpoints of solubility, applicability and dryness of the resin component, the boiling point of the organic solvent is preferably 120 to 300 ° C, more preferably 120 to 270 ° C, still more preferably 120 to 250 ° C, particularly preferably Is 120-230 degreeC. Specific examples of such organic solvents include amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone and γ-valerolactone; Ketone solvents such as cyclohexanone, cyclopentanone, and methyl ethyl ketone; Acetic acid ester solvents such as butyl acetate and amyl acetate; Carbonate solvents such as sulfur-containing solvents such as dimethyl sulfone, dimethyl sulfoxide and sulfolane, ethylene carbonate and propylene carbonate, and the like. Among them, N, N-dimethylacetamide (boiling point: 165 ° C), γ-butyrolactone (boiling point: 204 ° C), and N-methylpyrrolidone in view of excellent solubility in polyimide polymers and polyamides A solvent selected from the group consisting of (boiling point: 202 ° C.), butyl acetate (boiling point: 126 ° C.) and cyclopentanone (boiling point: 131 ° C.) light amyl acetate (boiling point: 149 ° C.) is preferable. As a solvent, 1 type may be used independently and may be used in combination of 2 or more type. In addition, when using 2 or more types of solvent, it is preferable to select the kind of solvent so that the boiling point of the solvent with the highest boiling point in the solvent used may fall in the said range.

The amount of the solvent may be selected so that the resin varnish can be handled, and there is no particular limitation. For example, the amount of the solvent is preferably 50 to 95% by mass, more preferably 70 to 95% by mass, More preferably, it is 80-95 mass%.

The transparent resin film of this invention is obtained by coating the said resin varnish on a support body, and predrying. The transparent resin film is laminated on the support so that peeling is possible. Peelable means that the shape can be maintained as a film and can be peeled from the support without being broken. Specifically, it means drying so that an appropriate amount of solvent remains by predrying. When the amount of residual solvent is too large here, the shape as a film cannot be maintained, and when the amount of residual solvent is too small, the adhesion with the support is too high and breaks upon peeling. The amount of suitable residual solvent changes depending on the kind of resin composition, a solvent, and a support body of a transparent resin film, and needs to adjust suitably. However, content of the solvent in a transparent resin film is 0.1 mass% or more with respect to the gross mass of a transparent resin film normally. Although the upper limit of solvent content in a transparent resin film will not be specifically limited if it is a range which can maintain a shape as a film, Usually, it is 50 mass% or less with respect to the gross mass of a transparent resin film. In addition, in this invention, the solvent content in a transparent resin film spreads over 120 degreeC-250 degreeC using the thermogravimetry-differential heat (TG-DTA) measuring apparatus, for example, as described in the Example mentioned later. The mass reduction rate (mass%) can be measured and calculated.

In the present invention, the support and the resin film must be peelable. However, when adhesive force is too weak and peels easily, another problem arises. For example, in an actual film forming apparatus, the support may be peeled off at the bent portion at the time of passage of the guide roll during conveyance of the laminate. Therefore, it is preferable not to peel even if a laminated body is wound 180 degree to the cylindrical rod of diameter 200mm, It is more preferable not to peel even if a laminated body is wound 180 degrees to the cylindrical rod of diameter 160mm, The diameter 120 It is more preferable not to peel even if a laminated body is wound by 180 degree to the cylindrical rod of mm, It is still more preferable not to peel even if a laminated body is wound 180 degree to the cylindrical rod of diameter 100mm, and it is a cylinder of 60 mm diameter It is especially preferable not to peel even if a laminated body is wound 180 degree | times to the rod of a shape.

Although the thickness of a transparent resin film may be suitably determined according to the use of a transparent resin film, etc., Usually, it is 10-500 micrometers, Preferably it is 15-200 micrometers, More preferably, it is 20-130 micrometers. When the thickness of a transparent resin film exists in the said range, the flexibility of a transparent resin film is favorable.

In this invention, Preferably, a transparent resin film is 1.0% or less of haze, 85% or more of total light transmittance, and yellow index (yellowness) 4 or less. If such a requirement is satisfied, it can be used as a favorable resin film with high transparency. The measuring method of a haze, total light transmittance, and a yellow index (yellowness) is described in detail in an Example. The haze is the same as the opacity of the resin film, and of course, less is better, preferably 0.7% or less, and more preferably 0.5% or less. The total light transmittance is the transmittance of the light rays passing through the film, and it is better that the transparency is close to 100%, preferably 85% or more, more preferably 87% or more, and still more preferably 89% or more. When the total light transmittance is in the above range, for example, when applied to a liquid crystal display device, the same brightness can be obtained on the viewing side even if the power of a light source such as a backlight is lowered compared to the case where the transmittance is low, and energy saving is achieved. We can contribute as environment-adaptive technique in fire. In addition, the yellow index represents yellowness, and the smaller the yellowness, the better the performance, preferably 3 or less, more preferably 2.5 or less, still more preferably 2.2 or less, and particularly preferably 2.0 or less.

Protective film

The laminated body of this invention may also contain the protective film bonded to the said transparent resin film. The protective film is bonded to the surface without a support of the transparent resin film. When winding up a laminated body in roll shape, when there exists a problem in winding properties, such as blocking, you may bond a protective film to the surface on the opposite side to the transparent resin film of a support body in addition to the above. The protective film bonded to a transparent resin film is a film for temporarily protecting the surface of a transparent resin film, and it is not specifically limited as long as it is a peelable film which can protect the surface of a transparent resin film. For example, Polyester resin films, such as a polyethylene terephthalate, a polybutylene terephthalate, and a polyethylene naphthalate; Polyolefin resin films, such as polyethylene and a polypropylene film, an acrylic resin film, etc. are mentioned, It is preferable to select from the group which consists of a polyolefin resin film, a polyethylene terephthalate resin film, and an acrylic resin film. When the protective film is bonded to both surfaces of a laminated body, the protective film of each surface may mutually be same or different.

Although the thickness of a protective film is not specifically limited, Usually, 10-100 micrometers, Preferably it is 10-80 micrometers, More preferably, it is 10-50 micrometers. When the protective film is bonded to both surfaces of a laminated body, the thickness of the protective film of each surface may be same or different.

Laminate film roll

In this invention, the thing by which the said laminated body (support body, a transparent resin film, and a protective film as needed) were wound by roll core in roll shape is called laminated body film roll. In the continuous manufacture, the laminate film roll is often stored in the form of a film roll once from space or other constraints, and the laminate film roll is one of them. In the form of a laminated film roll, since a laminated body is wound up more tightly, the cloudy cause substance on a support body becomes easy to be transferred on a transparent resin film. However, when the support having the predetermined logarithmic contact angle of the present invention is used, the clouding material from the support is hardly transferred to the transparent resin film, and even if it is wound around the laminate film roll, clouding is unlikely to occur.

As a material which comprises the core of a laminated film roll, a polyethylene resin, a polypropylene resin, a polyvinyl chloride resin, a polyester resin, an epoxy resin, a phenol resin, a melamine resin, a silicon resin, a polyurethane resin, a polycarbonate resin, for example Synthetic resins such as ABS resin; Metals such as aluminum; Fiber-reinforced plastics (FRP: composite material in which fibers such as glass fibers are contained in plastics to improve strength); The core forms a shape such as a cylindrical shape or a cylindrical shape, and the diameter thereof is, for example, 80 to 170 mm. In addition, the diameter (diameter after winding) of a film roll is although it does not specifically limit, Usually, it is 200-800 mm.

This invention also provides the method of manufacturing the said laminated body. The manufacturing method of the said laminated body,

a) The resin varnish obtained by mixing and stirring the resin composition for forming a transparent resin film with a solvent is apply | coated on the support body whose martens hardness of the side which coats a resin varnish is 300 N / mm <2> or more, and at that time, When the logarithmic contact angle of the laminated surface with the said transparent resin film is A, and the laminated surface is wash | cleaned with (gamma) -butyrolactone, and the logarithmic contact angle measured after drying is set to B, | BA | is 8.0 degrees or less; And

b) removing the solvent by drying the applied resin varnish and forming a layer of a transparent resin film on the support;

It includes. In addition, when forming a protective film,

c) It is necessary to further include bonding a protective film to the surface on the opposite side to the support body of the transparent resin film formed on the support body.

The laminated body of this invention only controls the logarithmic contact angle of the surface of the side which contact | connects the transparent resin film of a support body, and the cloudiness of the transparent resin film resulting from a support body, especially the white cloudiness of a transparent polyimide-type film is reduced, The yield is greatly improved, and the productivity is improved.

Window film substrate

The transparent resin film obtained by peeling a support body from the laminated body of this invention is further dried (this drying), and can be used as a window film base material by reducing the amount of residual solvent. Although there is no restriction | limiting in particular in the process of this drying, It is preferable to dry, fixing the width direction with a transverse stretching machine etc. in order to prevent the deformation at the time of drying. When this drying is performed by a horizontal stretching machine, you may extend | stretch a transparent resin film, may process by equal magnification, or may shrink | contract. In addition, although the amount of residual solvent of a window film base material may be suitably adjusted according to the calculated | required physical property, it is 3.0% or less normally, Preferably it is 1.5% or less, More preferably, it is 1.0% or less, Especially preferably, it is 0.8% or less. When the amount of residual solvent is less than the above upper limit, since the film surface is not too soft and a wound hardly occurs, handling of a film becomes easy in a later process. Here, a window film is a member arrange | positioned at the visual side of an image display apparatus, and a protective film, another functional layer, or a film may be arrange | positioned further on the surface of a window film. In addition, a window film base material is a base film for window films, and is normally used as a window film by providing a window hard coating layer for the purpose of the improvement of surface hardness. Depending on the purpose of use and the characteristics of the transparent film, the window film base material may be used as the window film as it is. As the window film base material, a transparent polyimide film or a transparent polyamide film is suitable.

Window film

The window film comprises a window hard coating layer on at least one surface of the window film substrate. The window film is not as rigid as conventional glass and has a flexible characteristic. A window film base material and a window film having a window hard coating layer on at least one surface of the window film base material protect other components of the image display device including the window film base material from external impact or changes in ambient temperature and humidity. It will play a role. In addition, the hard coating layer has a function of improving the surface hardness of the transparent substrate. In addition, the hard coat layer has light transmittance and flexibility.

The thickness of the window hard coating layer of the said window film is not specifically limited, For example, 5-100 micrometers may be sufficient. When the thickness of the window hard coating layer is 5 µm or more, it is possible to ensure sufficient surface hardness, and in the case of 100 µm or less, the flex resistance does not drop excessively, and a problem of curl generation due to curing shrinkage is less likely to occur. have.

The window hard coating layer may be formed by curing a composition for hard coating containing a reactive material that forms a crosslinked structure by irradiating light or thermal energy.

The window hard coating layer may be formed by curing a composition for window hard coating containing a photocurable (meth) acrylate monomer or an oligomer and a photocurable epoxy monomer or an oligomer simultaneously.

In addition to the photocurable (meth) acrylate monomer and oligomer mentioned above, the composition for window hard coating contains a solvent and a photoinitiator as needed. In addition, the composition for window hard coating may contain additives, such as an inorganic filler, a leveling agent, a stabilizer, antioxidant, a UV absorber, surfactant, a lubricating agent, and an antifouling agent, in the range which does not impair the effect of this invention.

The window hard coating layer may be formed by applying the above-described composition for window hard coating to at least one surface of a window film substrate and curing the same.

Optical stack

Another example of the present invention is an optical laminate including the window film described above, and specifically, one layer selected from the group consisting of a polarizing plate and a touch sensor on one surface of the window film provided with the window hard coating layer of the present invention. It relates to an optical laminate further comprising. In addition, the window film may include a polarizing plate or a touch sensor with an adhesive layer interposed therebetween as necessary.

In addition, at least one surface of the window film or the polarizing plate may be provided with a colored light shielding pattern printed around an edge, and the light shielding pattern may be in the form of a single layer or a multilayer. In addition, the polarizing layer may be bonded to one surface of the window film with a direct or adhesive bonding layer interposed therebetween. For example, the polarizing layer may extend continuously over the non-display area or the bezel portion, and includes a polyvinyl alcohol polarizer and a protective film attached to at least one surface of the polyvinyl alcohol polarizer. It may be.

As another example of the present invention, the polarizing layer and the touch sensor are integrated on one surface of the window film, and the arrangement order of the polarizing layer and the touch sensor is not limited, and the window film, the polarizing layer, the touch sensor, and the display panel may be It may be arranged in order, or may be arranged in the order of a window film, a touch sensor, a polarizing layer and a display panel. When arranged in the order of a window film, a polarizing layer, a touch sensor, and a display panel, when the image display apparatus is seen from the visual recognition side, since a touch sensor exists in the lower side of a polarizing layer, the pattern of a touch sensor is hard to be recognized. . In such a case, it is preferable that the front phase difference of the board | substrate of a touch sensor is ± 2.5 nm or less. As such a raw material, as a non-stretched film, the film of 1 or more types of materials chosen from the group which consists of raw materials, such as a triacetyl cellulose, a cycloolefin, a cycloolefin copolymer, a polynorbornene copolymer, may be sufficient, for example. Meanwhile, only the pattern without the substrate of the touch sensor may have a structure transferred to the window film and the polarizing layer.

Although the said polarizing layer and a touch sensor can be arrange | positioned between a window film and a display panel with a transparent adhesive layer or a transparent adhesive bond layer, a transparent adhesive layer is suitable. When arranged in the order of a window film, a polarizing layer, a touch sensor, and a display panel, a transparent adhesive layer may be located between a window film and a polarizing layer, and between a touch sensor and a display panel. When arranged in the order of a window film, a touch sensor, a polarizing layer, and a display panel, a transparent adhesive layer can be located between a window film and a touch sensor, between a touch sensor and a polarizing layer, and between a polarizing layer and a display panel. have.

The thickness of the said transparent adhesive layer is not specifically limited, For example, 1-100 micrometers may be sufficient. In the transparent adhesive layer which concerns on this invention, it is preferable that the thickness of a lower adhesion layer is more than the thickness of an upper adhesion layer, and viscoelasticity is 0.2 Mpa or less at -20-80 degreeC. In this case, the noise generated by the interference between the touch sensor and the display panel can be reduced, and the interfacial stress during bending can be alleviated to prevent the destruction of the base material at the upper and lower parts. More preferably, the viscoelasticity may be 0.01 to 0.15 MPa in terms of suppressing cohesive failure of the pressure-sensitive adhesive and at the same time relaxing the interfacial stress.

Polarizer

The polarizing plate laminated | stacked on the said window film may be the structure provided with the polarizer alone or the polarizer and the protective film affixed on at least one surface. The thickness of the said polarizing plate is not specifically limited, For example, 100 micrometers or less may be sufficient. If thickness is 100 micrometers or less, flexibility will hardly fall. 5-100 micrometers may be sufficient, for example within the said range.

The polarizer may be a film polarizer commonly used in the art, which is produced by a process including a step of swelling, dyeing, crosslinking, stretching, washing with water, drying, or the like of a polyvinyl alcohol-based film. As another example, It can form by apply | coating the composition for liquid crystal coating as a polarizing coating layer. The liquid crystal coating composition may include a polymerizable liquid crystal compound and a dichroic dye as a coating layer forming composition. For example, the polarizing coating layer may be coated with an alignment film forming composition on a substrate, to provide an alignment property to form an alignment film, and to apply a coating layer forming composition containing a liquid crystal compound and a dichroic dye onto the alignment film to form a liquid crystal coating layer. It can manufacture by forming. Such a polarizing coating layer can form a thin thickness compared with the polarizing plate containing the protective film affixed on both surfaces of a polyvinyl alcohol-type polarizer with an adhesive agent. The thickness of the polarizing coating layer may be 0.5 to 10 µm, preferably 2 to 4 µm.

Alignment film forming composition

The alignment layer forming composition may include an alignment agent, a photopolymerization initiator, and a solvent commonly used in the art. As the aligning agent, an aligning agent usually used in the art can be used without particular limitation. For example, a polyacrylate-based polymer, a polyamic acid, a polyimide-based polymer, or a polymer containing cinnamate groups can be used as the alignment agent, and when a photoalignment is applied, it is preferable to use a polymer containing cinnamate groups. Do.

Examples of the coating of the alignment layer forming composition include spin coating, extrusion molding, dip coating, flow coating, spray coating, roll coating, gravure coating, micro gravure coating, and the like. use. After the said alignment film formation composition is apply | coated and dried as needed, an orientation treatment is performed. The said orientation process can employ | adopt various well-known methods in the said field | area without limitation, Preferably, photo-alignment film formation can be used. A photoalignment film is obtained by apply | coating the composition for photoalignment film formation containing a polymer or monomer which has a photoreactive group, and a solvent to a base material normally, and irradiating polarized light (preferably polarized UV). A photo-alignment film is more preferable at the point which can arbitrarily control the direction of an orientation regulation force by selecting the polarization direction of the polarized light to irradiate.

The film thickness of the photoalignment film is usually 10 to 10,000 nm, preferably 10 to 1,000 nm, more preferably 500 nm or less, and still more preferably 10 nm or more. When it is in the said range, an orientation regulation force will fully express.

Polarizing Coating Layer Formation Composition

The polarizing coating layer may be formed by applying a polarizing coating layer forming composition. Specifically, the polarizing coating layer-forming composition is a composition (hereinafter referred to as composition B) containing one or more polymerizable liquid crystals (hereinafter sometimes referred to as polymerizable liquid crystals (B)) which become a host compound in addition to a dichroic dye. Case).

A "dichroic dye" means the pigment | dye which has the property which the absorbance in the long axis direction of a molecule | numerator differs from the absorbance in a short axis direction. As long as it has such a property, a dichroic dye does not have a restriction | limiting and may be a dye and a pigment may be sufficient as it. Two or more types of dyes may be used in combination, two or more types of pigments may be used in combination, and dyes and pigments may be used in combination.

It is preferable that a dichroic dye has maximum absorption wavelength ((lambda) _MAX ) in the range of 300-700 nm. As such a dichroic dye, an acridine pigment, an oxazine pigment, a cyanine pigment, a naphthalene pigment, an azo pigment, and an anthraquinone pigment is mentioned, Especially, an azo pigment is preferable. As an azo pigment | dye, a monoazo pigment | dye, a bis azo pigment | dye, a tris azo pigment | dye, a tetrakis azo pigment | dye, and a stilbenazo pigment | dye are mentioned, A bis azo pigment | dye and a tris azo pigment | dye are preferable.

It is preferable that it is a smectic phase, and, as for the liquid crystal state represented by a polymeric liquid crystal (B), it is more preferable that it is a higher order smectic phase from the point which can manufacture the polarizing layer with higher orientation order degree. The polymerizable liquid crystal (B) showing a smectic phase is called a polymerizable smectic liquid crystal compound. The polymerizable liquid crystal (B) can be used alone or in combination. Moreover, when combining 2 or more types of polymerizable liquid crystals, at least 1 type is preferable if it is a polymerizable liquid crystal (B), and it is more preferable if 2 or more types are polymerizable liquid crystals (B). By combining, the liquid crystal can be temporarily retained even at a temperature below the liquid crystal-crystal phase transition temperature. The polymerizable liquid crystal (B) is, for example, Lub et al. Recl. Trav. Chim. It is manufactured by the well-known method described in Pays-Bas, 115, 321-328 (1996) or Japanese Patent No. 4719156. Although content of the dichroic dye in composition B can be suitably adjusted according to the kind of dichroic dye, etc., Preferably it is 0.1 mass part or more and 50 mass parts or less with respect to 100 mass parts of polymerizable liquid crystals (B), More preferably, Is 0.1 mass part or more and 20 mass parts or less, More preferably, they are 0.1 mass part or more and 10 mass parts or less. When content of a dichroic dye is in the said range, it can superpose | polymerize, without disperse | distributing the orientation of a polymeric liquid crystal (B), and the tendency which inhibits the orientation of a polymeric liquid crystal (B) is small.

It is preferable that composition B contains a solvent. Generally, since a smectic liquid crystal compound has a high viscosity, the composition containing a solvent is easy to apply | coat, and as a result, it is easy to form a polarizing film in many cases. As a solvent, the thing similar to the solvent contained in the orientation polymer composition mentioned above can be mentioned, It can select suitably according to the solubility of a polymeric liquid crystal (B) and a dichroic dye. Content of a solvent becomes like this. Preferably it is 50-98 mass% with respect to the total amount of the composition B. If it reduces, solid content in the composition B becomes like this. Preferably it is 2-50 mass%.

It is preferable that composition B contains at least 1 leveling agent. The leveling agent has a function of adjusting the fluidity of the composition B and flattening the coating film obtained by applying the composition B, and specifically, a surfactant may be mentioned. When composition B contains a leveling agent, the content becomes like this. Preferably it is 0.05 mass part or more and 5 mass parts or less, More preferably, it is 0.05 mass part or more and 3 mass parts or less with respect to 100 mass parts of polymeric liquid crystals. When content of a leveling agent exists in said range, it is easy to horizontally align a polymeric liquid crystal, and there exists a tendency for the polarizing layer obtained to become smoother. When content of the leveling agent with respect to a polymeric liquid crystal is in the said range, there exists a tendency which a nonuniformity does not produce very much in the polarizing layer obtained.

It is preferable that composition B contains 1 or more types of polymerization initiators. A polymerization initiator is a compound which can start the polymerization reaction of a polymeric liquid crystal (B), and a photoinitiator is preferable at the point which can start a polymerization reaction under lower temperature conditions. Specifically, the photoinitiator which can generate | occur | produce an active radical or an acid by the action of light is mentioned, Especially the photoinitiator which generate | occur | produces a radical by the action of light is preferable. Examples of the polymerization initiator include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts and sulfonium salts.

When composition B contains a polymerization initiator, although the content can be suitably adjusted according to the kind and quantity of the polymeric liquid crystal contained in the composition, Preferably it is 0.1-30 mass parts with respect to 100 mass parts of polymeric liquid crystals. More preferably, it is 0.5-10 mass parts, More preferably, it is 0.5-8 mass parts. If content of a polymerization initiator exists in this range, it can superpose | polymerize without disturbing the orientation of a polymeric liquid crystal (B). When composition B contains a photoinitiator, the said composition may further contain the photosensitizer. When composition B contains a photoinitiator and a photosensitizer, the polymerization reaction of the polymeric liquid crystal contained in this composition can be accelerated | stimulated more. Although the usage-amount of a photosensitizer can be suitably adjusted according to the kind and quantity of a photoinitiator and a polymeric liquid crystal, Preferably it is 0.1-30 mass parts, More preferably, it is 0.5-10 mass with respect to 100 mass parts of polymeric liquid crystals. Part, more preferably 0.5 to 8 parts by mass.

In order to advance the polymerization reaction of a polymeric liquid crystal more stably, the composition B may contain a suitable quantity of polymerization inhibitor, and thereby, it becomes easy to control the progress of the polymerization reaction of a polymeric liquid crystal. When composition B contains a polymerization inhibitor, the content can be suitably adjusted according to the kind and quantity of a polymeric liquid crystal, the usage-amount of a photosensitizer, etc., Preferably it is 0.1 with respect to 100 mass parts of polymeric liquid crystals. It is -30 mass parts, More preferably, it is 0.5-10 mass parts, More preferably, it is 0.5-8 mass parts. If content of a polymerization inhibitor is in this range, it can superpose | polymerize without disturbing the orientation of a polymeric liquid crystal.

Manufacturing method of polarizing coating layer

A polarizing coating layer is normally formed by apply | coating a polarizing coating layer forming composition on the base material on which the orientation process was performed, and polymerizing the polymerizable liquid crystal in the obtained coating film. The method of apply | coating the said polarizing coating layer forming composition is not limited. Examples of the orientation treatment include those exemplified above. A dry film is formed by apply | coating a polarizing coating layer forming composition and drying-drying a solvent on the conditions which the polymerizable liquid crystal contained in the obtained coating film does not superpose | polymerize. As a drying method, a natural drying method, a ventilation drying method, heat drying, and a vacuum drying method are mentioned. When a polymerizable liquid crystal is a polymeric smectic liquid crystal compound, it is preferable to make the liquid crystal state of the polymeric smectic liquid crystal compound contained in a dry film into a nematic phase (nematic liquid crystal state), and then transfer to a smectic phase. In order to form a smectic phase via the nematic phase, for example, the polymerizable smectic liquid crystal compound contained in the dry coating is heated to a temperature above the temperature at which the phase transitions into the liquid crystal state of the nematic phase, and then the polymerizable property is subsequently obtained. The method in which a smectic liquid crystal compound is cooled to a temperature exhibiting a liquid crystal state of a smectic phase is adopted. Subsequently, after making the liquid crystal state of the polymeric liquid crystal in a dry film into a smectic phase, the method of photopolymerizing a polymeric liquid crystal is demonstrated, maintaining the smectic phase liquid crystal state. In photopolymerization, the light irradiated to a dry film can be suitably selected according to the kind of photoinitiator contained in the said dry film, the kind of polymeric liquid crystal (especially the kind of photopolymerizer which a polymeric liquid crystal has), and its quantity, And the specific examples thereof include an active energy ray selected from the group consisting of visible light, ultraviolet light and laser light. Among these, ultraviolet light is preferable in that it is easy to control the progress of the polymerization reaction and in that it can be used as a photopolymerization device in a wide range of fields. By performing photopolymerization, the polymerizable liquid crystal is polymerized while maintaining a liquid crystal state of a smectic phase, preferably a higher order smectic phase, thereby forming a polarizing layer.

Retardation coating layer

In one embodiment of the present invention, the polarizing plate may include a phase difference coating layer. (Lambda) / 2 layer, (lambda) / 4 layer, a positive C layer, etc. are named generically according to an optical characteristic of retardation coating layer. The retardation coating layer is, for example, after coating a coating layer forming composition containing a liquid crystal compound on the substrate film subjected to the alignment treatment to form a liquid crystal coating layer, and then affixing the liquid crystal coating layer with a polarizing plate via an adhesive layer, Although it can form by peeling, it is not limited to this method. As the base film, the polymer film exemplified as the protective film can be used, and the base material surface on the side where the alignment film and the retardation layer are formed may be subjected to surface treatment before forming the alignment film. Since the said alignment film formation composition, its application | coating, drying method, etc. are the same as what was demonstrated by the polarizing coating layer, a base material is abbreviate | omitted in order to avoid duplication. The composition of the coating layer forming composition is the same as that described in the polarizing coating layer, except that the dichroic dye is not included. In addition, since the application | coating, drying, and hardening method of the said coating layer forming composition are also the same as what was demonstrated by the said polarizing coating layer, description is abbreviate | omitted in order to avoid duplication.

The thickness of the retardation coating layer may be 0.5 to 10 µm, preferably 1 to 4 µm.

In one embodiment of this invention, a retardation coating layer can adjust an optical characteristic according to the thickness of a coating layer, the orientation state of a polymeric liquid crystal compound, etc. Specifically, by adjusting the thickness of the retardation layer, a retardation layer that gives a desired in-plane retardation can be produced. The in-plane retardation value (in-plane retardation value, Re) is a value defined by Formula (1), and in order to obtain desired Re, what is necessary is just to adjust (DELTA) n and film thickness d.

Re = d × Δn (λ)... Equation (1), where Δn = nx-ny

(In Formula (1), Re represents an in-plane retardation value, d represents a film thickness, and Δn represents a birefringence. When considering the refractive index ellipsoid formed by the orientation of the polymerizable liquid crystal compound, The refractive indices, i.e., nx, ny and nz, are defined as follows: nx represents the main refractive index in a direction parallel to the substrate plane in the refractive index ellipsoid formed by the retardation layer, and ny represents the refractive index ellipsoid formed by the retardation layer. The refractive index in the direction parallel to the substrate plane in and perpendicular to the direction of nx, nz represents the refractive index in the direction perpendicular to the substrate plane in the refractive index ellipsoid formed by the phase difference layer. In the case of the λ / 4 layer, the in-plane retardation value Re (550) is in the range of 113 to 163 nm, preferably in the range of 130 to 150 nm. 300 nm Above, preferably in the range of 250~300㎚.)

Moreover, the phase difference layer which expresses the phase difference of the thickness direction can be produced according to the orientation state of a polymeric liquid crystal compound. Expressing the phase difference in the thickness direction indicates a characteristic in which the phase difference value Rth in the thickness direction becomes negative in Equation (2).

Rth = [(nx + ny) / 2-nz] × d... Formula (2)

(In formula (2), nx, ny, nz, and d are the same as the definition of the above.)

The in-plane retardation value Re (550) of the positive C layer is usually in the range of 0 to 10 nm, preferably in the range of 0 to 5 nm, and the retardation value Rth in the thickness direction is usually -10 to -300 nm. The range is preferably in the range of -20 to -200 nm. The polarizing plate of the present invention may have two or more retardation coating layers, and in the case of having two retardation coating layers, the first retardation coating layer is a λ / 4 layer for producing circularly polarized light and the second retardation coating layer is used to improve the color tone seen at an angle. May be a positive C layer. Further, the first retardation coating layer may be a positive C layer for improving the color tone seen at an angle, and the second retardation coating layer may be a λ / 4 layer for producing circularly polarized light.

Adhesive layer

In one embodiment of the present invention, the polarizing coating layer and the first retardation coating layer, or the first retardation coating layer and the second retardation coating layer can be bonded to each other via an adhesive or an adhesive. As an adhesive agent which forms an adhesive bond layer, an aqueous adhesive agent, an active energy ray curable adhesive agent, or a thermosetting adhesive agent can be used, Preferably it is an aqueous adhesive agent and an active energy ray curable adhesive agent. As an adhesive layer, the thing mentioned later can be used.

Adhesive layer

As an aqueous adhesive agent, the adhesive agent which consists of polyvinyl alcohol-type resin aqueous solution, an aqueous two-component urethane emulsion adhesive, etc. are mentioned. Especially, the aqueous adhesive which consists of aqueous solution of polyvinyl alcohol-type resin is used suitably. As polyvinyl alcohol-type resin, the polyvinyl alcohol-type copolymer obtained by saponifying the copolymer of vinyl acetate and the other monomer copolymerizable with this besides the vinyl alcohol homopolymer obtained by saponifying polyvinyl acetate which is a homopolymer of vinyl acetate. Or modified polyvinyl alcohol polymers obtained by partially modifying their hydroxyl groups. The aqueous adhesive may include a crosslinking agent such as an aldehyde compound (glyoxal or the like), an epoxy compound, a melamine compound, a methylol compound, an isocyanate compound, an amine compound, a polyvalent metal salt, or the like.

When using an aqueous adhesive agent, after bonding a coating layer, it is preferable to perform the drying process for removing the water contained in an aqueous adhesive agent.

The said active energy ray curable adhesive agent is an adhesive agent containing the curable compound hardened | cured by irradiation of active energy rays, such as an ultraviolet-ray, visible light, an electron beam, and an X-ray, Preferably it is an ultraviolet curable adhesive agent.

The curable compound may be a cation polymerizable curable compound or a radical polymerizable curable compound. As a cationic polymerizable curable compound, For example, an epoxy type compound (compound which has 1 or 2 or more epoxy groups in a molecule), an oxetane type compound (compound which has 1 or 2 or more oxetane rings in a molecule), Or a combination thereof. As a radically polymerizable curable compound, it is a (meth) acrylic-type compound (compound which has one or two or more (meth) acryloyloxy groups in a molecule | numerator), and the other vinyl type compound which has a radically polymerizable double bond, for example. Or a combination thereof. You may use a cationically polymerizable curable compound and a radically polymerizable curable compound together. The active energy ray curable adhesive usually further contains a cationic polymerization initiator and / or a radical polymerization initiator for initiating the curing reaction of the curable compound.

In bonding a coating layer, in order to improve adhesiveness, you may surface-treat the at least one bonding surface of the surface to adhere | attach. As the surface activation treatment, dry treatment such as corona treatment, plasma treatment, discharge treatment (glow discharge treatment, etc.), flame treatment, ozone treatment, UV ozone treatment, ionizing active line treatment (ultraviolet treatment, electron beam treatment, etc.); And wet treatments such as ultrasonic treatment, saponification treatment and anchor coating treatment using a solvent such as water or acetone. These surface activation processes may be performed independently, or may combine 2 or more.

The thickness of the said adhesive layer can be adjusted according to the adhesive force, Preferably it is 0.1-10 micrometers, More preferably, it may be 1-5 micrometers. In one embodiment of the present invention, in the case of a configuration in which a plurality of the adhesive layers are used, they may be made of the same material or of different materials, and may have the same thickness or different thicknesses.

Adhesive layer

An adhesive layer can be comprised by the adhesive composition which has resin, such as (meth) acrylic-type resin, rubber type resin, polyurethane type resin, polyester type resin, silicone type resin, and polyvinyl ether type resin as a main component. Especially, the adhesive composition which uses polyester resin or (meth) acrylic-type resin which is excellent in transparency, weather resistance, heat resistance, etc. as a base polymer is suitable. An active energy ray hardening type and a thermosetting type may be sufficient as an adhesive composition.

As adhesive resin used by this invention, the thing of the range of 300,000-4 million in weight average molecular weight is used normally. When durability, especially heat resistance are considered, the weight average molecular weight becomes like this. Preferably it is 500,000-3 million, More preferably, it is 650,000-2 million. When a weight average molecular weight is larger than 300,000, it is preferable at the point of heat resistance, and when a weight average molecular weight is smaller than 4 million, it is also preferable at the point where adhesiveness and adhesive force fall. In addition, a weight average molecular weight is measured by GPC (gel permeation chromatography) and says the value computed by polystyrene conversion.

In addition, the adhesive composition may contain a crosslinking agent. As a crosslinking agent, an organic type crosslinking agent and a polyfunctional metal chelate can be used. As an organic type crosslinking agent, an isocyanate type crosslinking agent, a peroxide type crosslinking agent, an epoxy type crosslinking agent, an imine type crosslinking agent, etc. are mentioned. A polyfunctional metal chelate is a thing in which a polyvalent metal is covalently bonded or coordinated with an organic compound. Examples of the polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like. have. Examples of the atoms in the organic compound to be covalently bonded or coordinated include oxygen atoms, and examples of the organic compound include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, ketone compounds, and the like.

When it contains a crosslinking agent, the usage-amount is preferably 0.01-20 mass parts, More preferably, it is 0.03-10 mass parts with respect to 100 mass parts of adhesive resin. When the crosslinking agent exceeds 0.01 parts by mass, the cohesion force of the pressure-sensitive adhesive layer tends not to be insufficient, and there is little possibility that foaming occurs during heating. On the other hand, when the crosslinking agent is less than 20 parts by mass, the moisture resistance is sufficient, Peeling becomes difficult to occur.

As an additive, it is preferable to mix | blend a silane coupling agent. Examples of the silane coupling agent include silicon having an epoxy structure such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. compound; Amino group-containing silicon compounds such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane and N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane; 3-chloropropyltrimethoxysilane; (Meth) acryl group containing silane coupling agents, such as acetoacetyl group containing trimethoxysilane, 3-acryloxypropyl trimethoxysilane, and 3-methacryloxypropyl triethoxysilane; Isocyanate group containing silane coupling agents, such as 3-isocyanatopropyl triethoxysilane, etc. are mentioned. The silane coupling agent can give durability, especially the effect of suppressing peeling under a humidified environment. The amount of the silane coupling agent used is preferably 1 part by mass or less, more preferably 0.01 to 1 part by mass, and still more preferably 0.02 to 0.6 part by mass with respect to 100 parts by mass of the adhesive resin.

Moreover, the adhesive composition may contain other well-known additives, For example, in an adhesive composition, powder, such as a coloring agent and a pigment, dye, surfactant, a plasticizer, a tackifier, a surface lubricant, a leveling agent, a softening agent , Antioxidants, antioxidants, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, particulates, foils, and the like can be appropriately added depending on the intended use. Moreover, you may employ | adopt the redox system which added the reducing agent within the range which can be controlled.

The thickness of an adhesive layer is not specifically limited, For example, about 1-100 micrometers, Preferably it is 2-50 micrometers, More preferably, it is 3-30 micrometers. By making thickness of an adhesive layer thin, the total amount of the acid in an adhesive layer falls. Thereby, an acid component becomes difficult to corrode the wiring of a board | substrate. In addition, the adhesive layer which a 2nd layer has can be adjusted with the thickness of the flexible printed circuit board which fits.

Protective layer

In one Embodiment of this invention, the said polarizing plate may be a form which has at least 1 or more protective layers, and when one side of the polarizer which comprises a polarizing plate, or the polarizer has a phase difference layer, it is in the surface opposite to the polarizer of a phase difference layer. Can be located.

There is no restriction | limiting in particular as a protective layer as long as it is a film excellent in transparency, mechanical strength, thermal stability, moisture shielding property, isotropy, etc. Specifically, polyester film, such as polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate; Cellulose films such as diacetyl cellulose and triacetyl cellulose; Polycarbonate film; Acrylic films such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene films such as polystyrene and acrylonitrile-styrene copolymers; Polyolefin-based films such as cycloolefin, cycloolefin copolymer, polynorbornene, polypropylene, polyethylene, and ethylene propylene copolymer; Vinyl chloride film; Polyamide films such as nylon and aromatic polyamides; Imide film; Sulfone film; Polyether ketone film; Polyphenylene sulfide films; Vinyl alcohol film; Vinylidene chloride-based film; Vinyl butyral film; Arylate film; Polyoxymethylene film; Urethane film; Epoxy film; Silicone film etc. are mentioned. Among these, especially the cellulose type film which has the surface saponified by alkali etc. is preferable in consideration of polarization characteristic or durability. The protective layer may also have an optical compensation function such as a phase difference function.

The protective layer may have been subjected to an easy-adhesion process for improving adhesion to the surface to be bonded to the polarizer or the retardation coating layer. The easily-adhesive treatment is not particularly limited as long as it can improve the adhesive strength, and examples thereof include dry treatment such as primer treatment, plasma treatment, and corona treatment; Chemical treatments such as alkali treatment (saponification treatment); Low pressure UV treatment; and the like.

Touch sensor

The touch sensor has a substrate, a lower electrode provided on the substrate, an upper electrode facing the lower electrode, an insulating layer sandwiched between the lower electrode and the upper electrode.

The base material can employ | adopt various things, if it is a flexible resin film which has light transmittance. For example, as a base material, the film illustrated as a material of the above-mentioned transparent base material can be used.

The lower electrode has, for example, a plurality of small electrodes having a square shape in plan view. The plurality of small electrodes are arranged in a matrix.

Further, the plurality of small electrodes are connected to adjacent small electrodes in one diagonal direction of the small electrode to form a plurality of electrode strings. The plurality of electrode strings are connected to each other at the end, and the capacitance between adjacent electrode strings can be detected.

The upper electrode has, for example, a plurality of small electrodes of square shape in plan view. The plurality of small electrodes are complementarily arranged in a matrix at positions where the lower electrodes are not arranged in plan view. That is, the upper electrode and the lower electrode are arranged without a gap in plan view.

Further, the plurality of small electrodes are connected to neighboring small electrodes in the other diagonal direction of the small electrode to form a plurality of electrode strings. The plurality of electrode strings are connected to each other at the end, and the capacitance between adjacent electrode strings can be detected.

The insulating layer insulates the lower electrode and the upper electrode. As a material for forming the insulating layer, a material commonly known as a material for the insulating layer of the touch sensor can be used.

In addition, in this embodiment, although the touch sensor was demonstrated as what is what is called a projected capacitive touch sensor, in the range which does not impair the effect of this invention, other touch sensors, such as a film resistance method, are employable. It may be.

Shading pattern

The light blocking pattern may be provided as at least a portion of a bezel or a housing of a window film or a display device to which the window film is applied. For example, each wiring of the display device may be hidden by the light shielding pattern and may not be visually recognized by the user. The color and / or material of the light shielding pattern is not particularly limited, and may be formed of a resin material having various colors such as black, white, and gold. For example, the light shielding pattern may be formed of a resin material such as an acrylic resin, an ester resin, an epoxy resin, polyurethane, silicone, or the like, in which a pigment for realizing color is mixed. The material and thickness of the light blocking pattern may be determined in consideration of protection and flexible characteristics of the window film or the display device. Moreover, these can also be used individually or in mixture of 2 or more types.

EXAMPLE

Hereinafter, the present invention will be described in more detail with reference to Examples. "%" And "part" in an example are mass% and a mass part unless there is particular notice. The present invention is not limited to these examples.

Preparation Example 1 Preparation of Transparent Polyimide Polymer

A reactor equipped with a silica gel tube, a stirring device, and a thermometer in a separable flask, and an oil bath were prepared. In this flask, 75.52 g of 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ( TFMB) 54.44g. 519.84 g of N, N-dimethylacetamide (DMAc) was added while stirring this at 400 rpm, and stirring was continued until the contents of the flask became a uniform solution. Subsequently, stirring was continued for 20 hours, and it was made to react so that the temperature in a container might be in the range of 20-30 degreeC using an oil bath, and it reacted and produced the polyamic acid. After 30 minutes, the stirring speed was changed to 100 rpm. After stirring for 20 hours, the reaction system temperature was returned to room temperature, and 649.8 g of DMAc was added to adjust the polymer concentration to 10% by weight. Furthermore, 32.27 g of pyridine and 41.65 g of acetic anhydride were added, and it stirred at room temperature for 10 hours and imidated. The polyimide varnish was taken out from the reaction vessel. The obtained polyimide varnish was dripped in methanol, reprecipitation was carried out, the obtained powder was heat-dried, the solvent was removed, and the transparent polyimide polymer was obtained as solid content. The GPC measurement of the obtained polyimide polymer showed a weight average molecular weight of 360,000.

Preparation Example 2 Preparation of Transparent Polyamide-imide Polymer

In a nitrogen gas atmosphere, 50 g (156.13 mmol) of TFMB and 642.07 g of DMAc were added to a 1 L separable flask equipped with a stirring blade, and TFMB was dissolved in DMAc while stirring at room temperature. Next, 20.84 g (46.91 mmol) of 6FDA was added to the flask, and the mixture was stirred at room temperature for 3 hours. Then, 9.23 g (31.27 mmol) of 4,4'-oxybis (benzoyl chloride) (OBBC), followed by 15.87 g (78.18 mmol) of terephthaloyl chloride (TPC) were added to the flask and at room temperature. It stirred for 1 hour. Subsequently, 9.89 g (106.17 mmol) of 4-methylpyridine and 14.37 g (140.73 mmol) of acetic anhydride were added to the flask, and after stirring for 30 minutes at room temperature, the temperature was raised to 70 ° C. using an oil bath. It stirred for the time and obtained the reaction liquid.

The obtained reaction liquid was cooled to room temperature, poured into a large amount of methanol, and the precipitate which precipitated was taken out, and after immersing in methanol for 6 hours, it wash | cleaned with methanol. Next, the precipitate was dried under reduced pressure at 100 ° C to obtain a transparent polyamideimide polymer. When the GPC measurement of the obtained polyamide-imide type polymer was performed, the weight average molecular weight was 420,000.

Preparation Example 3 Preparation of Silica Sol

When using an amorphous silica sol having a BET diameter (average primary particle size measured by the BET method) 27 nm produced by the sol-gel method and using solvent substitution, γ-butyrolactone (hereinafter referred to as GBL) Yes) A substituted silica sol was prepared. The obtained sol was filtered through a 10 μm membrane filter to obtain a GBL substituted silica sol. In all obtained GBL substituted silica sol, content of the silica particle was 30-32 mass%.

Example 1

The transparent polyimide-based polymer obtained in Production Example 1 was dissolved in a mixed solvent obtained by mixing γ-butyrolactone (GBL) and DMAc in a 1: 9 ratio at a solid content concentration of 16.5% to obtain a resin varnish. The resin varnish was 193 µm thick (PET 188 µm + hard coating layer 5 µm), width 900 mm, Martens hardness of 405 N / mm 2 on the cast film forming surface side (ie, hard coating layer surface side), and the logarithmic contact angle difference between the cast film forming surfaces ( | BA |) It is apply | coated to the polyethylene terephthalate (PET) film support body (support A: base resin = PET, HC processing oil) with the elongate-shaped hard coating layer of 0.1 degrees by 870mm in width by the casting method. It was unveiled. The solvent was removed from the resin solution by passing the film-formed resin varnish through a furnace having a length of 0.4 m / min in a length of 12 m in which the temperature was set to be 70 ° C to 120 ° C stepwise to form a transparent resin film (thickness 80 Μm) was formed. Thereafter, a protective film (Toray Tech (registered trademark) 7332K manufactured by Toray Film Processing Co., Ltd., a polyolefin protective film having a weak adhesive strength) is bonded to the transparent resin film, and the PET film has a protective film, a transparent resin film, and a hard coating layer. The film-like laminated body comprised is wound up to the roll core, and it was set as roll shape.

Peel test of laminate

The laminated body obtained by the cylindrical rod of a predetermined diameter is wound 180 degree | times, and after leaving still for 1 minute in that state, it is visually confirmed whether peeling generate | occur | produces between a support body and a transparent resin film. If delamination occurs even in a part, it is called occurrence of delamination.

When the peeling test was done with the laminated body obtained in Example 1, peeling did not generate | occur | produce in the whole when it wound 180 degree | times on each cylindrical rod of diameter 200mm, 160mm, 120mm, 100mm, and 60mm.

The support body A was peeled off, unwinding the laminated body wound up in roll shape in the above, and the laminated body comprised from a transparent resin film and a protective film was wound up.

While unwinding the laminated body of the transparent resin film and protective film wound up in roll shape above, the protective film was peeled off and white cloudiness was evaluated as follows. In addition, wound evaluation, haze, total light transmittance, a yellow index, and the amount of residual solvent were also measured as described below. The results are shown in Table 1.

Cloudiness evaluation

In the transparent resin film after peeling from a support body, after wiping a part of surface of a support body with the waste for cleaning room (Sabi and minimax (registered trademark), wiping cloth made from KB Siren Co., Ltd.), HID portable search made from POLARION company Using light PS-X1 (light beam 3,400 lumens), the external appearance (cloudiness) of the film was visually evaluated according to the following evaluation criteria. The light is irradiated at a lying angle of about 20 to 70 degrees with respect to the film surface. The direction to visually recognize is from the substantially top (an angle of 90 degrees from a resin film surface) of the surface of the transparent resin film to evaluate. In the case where there is turbidity, the above wiping trace is confirmed. Moreover, when the protective film is laminated | stacked on the surface opposite to the support body of a transparent resin film, a protective film is peeled off and the presence or absence of turbidity is confirmed.

<Evaluation standard of cloudiness>

(Circle): The trace which wiped off the surface of the transparent resin film was not able to be confirmed.

(Triangle | delta): The trace which wiped off the surface of the transparent resin film was able to confirm a little.

X: The trace which wiped off the surface of the transparent resin film was able to be confirmed clearly.

Wound evaluation

HID portable search light PS-X1 (beam 3,400 lumens) made by POLARION was irradiated to the surface on the opposite side to the support of the transparent resin film peeled from the support, and the presence or absence of the wound was visually confirmed. At this time, light was first irradiated from the flow direction of the film to confirm the presence of a wound, and then irradiated from the width direction to confirm the wound. In addition, light is irradiated at the lying angle of about 20-70 degrees with respect to the film surface. The direction to visually recognize is from the substantially top (an angle of 90 degrees from a resin film surface) of the surface of the transparent resin film to evaluate. Moreover, when the protective film is laminated | stacked on the surface opposite to the support body of a transparent resin film, a protective film is peeled off and the presence or absence of a wound is confirmed.

Evaluation standard

◎: wound is not recognized

○: the wound is slightly acknowledged

X: The wound is clearly recognized.

The results of the wound evaluations are shown in Table 1.

Haze

The haze of the transparent resin film was measured by the fully automatic direct reading haze computer HGM-2DP by Suga Test Machine Co., Ltd. based on JISK7105: 1981. The results are shown in Table 1. In addition, when the protective film is laminated | stacked on the surface opposite to the support body of a transparent resin film, a protective film is peeled off and haze is measured.

Total light transmittance

The total light transmittance of the transparent resin film was measured by the fully automatic direct reading haze computer HGM-2DP by Suga Test Machine Co., Ltd. based on JISK7105: 1981. The results are shown in Table 1. In addition, when the protective film is laminated | stacked on the surface opposite to the support body of a transparent resin film, a protective film is peeled off and a total light transmittance is measured.

Yellow index (yellowness: YI value)

The yellow index (yellowness: YI value) of the transparent resin film was measured with the ultraviolet-visible near-infrared spectrophotometer V-670 by a Japanese spectrometer. After performing background measurement in the state without a sample, the transparent resin film was set to the sample holder, the transmittance | permeability measurement with respect to the light of 300-800 nm was performed, and tristimulus values (X, Y, Z) were calculated | required. The YI value was calculated based on the following formula. In addition, when the protective film is laminated | stacked on the surface opposite to the support body of a transparent resin film, a protective film is peeled off and a yellow index is measured.

YI value = 100 × (1.2769X-1.0592Z) / Y

Measurement method of residual solvent amount (mass%)

Thermogravimetry-Differential Heat (TG-DTA) Measurement

As a measuring device of TG-DTA, TG / DTA6300 made by Hitachi High-Tech Science Co., Ltd. was used. About 20 mg of sample was obtained from the produced transparent resin film. The sample is heated at a temperature increase rate of 10 ° C./min from room temperature to 120 ° C. and held at 120 ° C. for 5 minutes, and then the temperature is changed (heated) at 400 ° C. at a temperature increase rate of 10 ° C./min, thereby changing the mass of the sample. Was measured.

From the TG-DTA measurement result, the mass reduction rate S (mass%) over 120 to 250 degreeC was computed according to the following formula.

S (mass%) = 100- (W1 / W0) * 100

[In formula, W0 is the mass of the sample after hold | maintaining at 120 degreeC for 5 minutes, and W1 is the mass of the sample in 250 degreeC.]

The computed mass reduction rate S was made into the residual solvent amount S (mass%) in a transparent resin film. In addition, when the protective film is laminated | stacked on the surface opposite to the support body of a transparent resin film, a protective film is peeled off and the amount of residual solvent is measured.

About the support, the following measurements were performed. The results are shown in Table 1.

Measurement conditions for logarithmic contact angle (before cleaning) A

1 mL of ultrapure water was dripped at the cast film forming surface of the support body, and the logarithmic contact angle was measured by the following method using the contact angle gauge (DM500) by Kyowa Interface Science. The same measurement is performed 10 times and an average value is shown in Table 1.

Method: Droplet method

Method: θ / 2 method

Curvature Correction: None

Liquid: Ultrapure Water

Liquid volume: 1mL

Measurement timing: 1000ms after dropping

Data processing: average value by measuring N = 10

Logarithmic contact angle (after cleaning) B

The γ-butyrolactone (GBL) was added dropwise to the cast film forming surface of the support so as to cover all the contact angle measurement points, and left standing for 1 minute, after which the clean room waste (KB Siren Co., Ltd. Sabina Minimax) was infiltrated with GBL. (Registered trademark) and wiping cloth) and wiped dry with a dry clean room waste until the rest of the GBL was not visually recognized. Then, it left still for 5 minutes and dried. Next, it measures using ultrapure water (1 mL) similarly to the said logarithmic contact angle A, and shows the average value of 10 measurements. In addition, the value of | B-A | was also calculated and shown in Table 1.

How to measure Martens hardness

After cut | disconnecting the said support body to the magnitude | size of 40 mm x 40 mm, the surface opposite to the cast film forming side was bonded to the glass of 40 mm x 40 mm through the adhesive layer of 20 micrometers of film thickness. 0.5mN using the Vickers indenter using the ultra-micro hardness tester (FISCHERSCOPE HM2000: Fischer Instruments Co., Ltd.) in the atmosphere of 23 degreeC and 55% RH on the surface which cast-forms the support body bonded to glass. After the load was applied at a pressurization rate of 5 seconds, the measurement was held for 5 seconds while maintaining a load of 0.5 mN. In addition, the measurement of martens hardness is performed with respect to the support body before cast film forming.

Measurement of arithmetic mean roughness (Ra) and maximum height (Rz)

Arithmetic mean roughness (Ra) and maximum height (Rz) were measured in accordance with JIS B0601-2001 using Surfcoder ET3000 manufactured by Kosaka Research Institute. The results are shown in Table 1. In addition, arithmetic mean roughness Ra and the maximum height Rz are measured with respect to the support body before cast film forming.

The transparent resin film was introduce | transduced into the drying furnace and further dried (this drying), peeling a protective film, unwinding the laminated body roll of the protective film of Example 1 and a transparent resin film. The temperature of the drying furnace was 200 degreeC, the conveyance speed was 1.0 m / min, and the drying time was 12 minutes. The transparent resin film after drying in the drying furnace bonded a protective film (Toray Tech (trademark) 7332K by Toray Film Processing Co., Ltd., polyolefin protective film of weak adhesive force) to one side, and wound up on the roll core. It was 1 mass% when the protective film was peeled off and the amount of residual solvent of the transparent resin film after this drying was measured. The transparent resin film obtained by this drying can also be used as a window film base material.

Example 2

The transparent polyamideimide-based polymer / silica particle mixed varnish having the composition shown in Table 1 by dissolving the transparent polyamideimide-based polymer obtained in Production Example 2 in GBL and adding the GBL substituted silica sol obtained in Production Example 3 and sufficiently mixing. (Hereinafter sometimes referred to as mixed varnish) was obtained. At that time, the mixed varnish was prepared so that the polyamide-imide polymer / silica particle concentration (the concentration relative to the total mass of the resin and the silica particles) would be 10% by mass. Then, the obtained mixed varnish was apply | coated to the support body A by width 870 mm, and was formed into a film. The solvent is removed from the resin solution by passing the film-forming mixed varnish through a furnace having a length of 0.4 m / min in a length of 12 m which is set so that the temperature is set to 70 ° C to 120 ° C stepwise to form a transparent resin film (50 µm thick). Formed. Thereafter, a protective film (Toray Tech (registered trademark) 7332K manufactured by Toray Film Processing Co., Ltd., a polyolefin protective film having a weak adhesive strength) is bonded to the transparent resin film, and the PET film has a protective film, a transparent resin film, and a hard coating layer. The film-like laminated body comprised is wound up to the roll core, and it was set as roll shape.

When the peeling test was done with the laminated body obtained in Example 2, peeling did not generate | occur | produce in the whole when it wound 180 degree around each cylindrical rod of diameter 200mm, 160mm, 120mm, 100mm, and 60mm.

The support body A was peeled off, unwinding the laminated body wound up in roll shape in the above, and the laminated body comprised from a transparent resin film and a protective film was wound up. By the method similar to Example 1, the white cloud, a wound | wound, total light transmittance, a yellow index, and the amount of residual solvent of the transparent resin film which peeled the protective film were evaluated. The results are shown in Table 1.

The transparent resin film was introduce | transduced into the drying furnace, and was further dried (this drying), peeling a protective film, unwinding the laminated body roll of the protective film of Example 2 and a transparent resin film. The temperature of the drying furnace was 200 degreeC, the conveyance speed was 1.0 m / min, and the drying time was 12 minutes. The transparent resin film after drying in the drying furnace bonded a protective film (Toray Tech (trademark) 7332K by Toray Film Processing Co., Ltd., polyolefin protective film of weak adhesive force) to one side, and wound up on the roll core. It was 0.6% when the protective film was peeled off and the amount of residual solvent of the transparent resin film after this drying was measured. The transparent resin film obtained by this drying can also be used as a window film base material.

Example 3

As a support, it was 193 micrometers in thickness (PET 188 micrometer + hard coating layer 5 micrometers), width 900mm, the Martens hardness of 406 N / mm <2> of the cast film forming surface side (namely, hard-coating layer surface side), and the logarithmic contact angle difference (| BA | A protective film and a transparent resin were treated in the same manner as in Example 1, except that a polyethylene terephthalate (PET) film (support B: base resin = PET, HC treated oil) having a long hard coating layer having a length of 1.7 ° was used. The roll of the laminated body which consists of a PET film which has a film and a hard coat layer was obtained.

In Example 3, although the logarithmic contact angle difference differs from the support body of Example 1, a logarithmic contact angle difference is performed by a general method, for example, adjustment of the hardening conditions of a hard coat layer, washing | cleaning after formation of a hard coat layer. In the following Examples and Comparative Examples, the logarithmic contact angle difference was adjusted in the same manner.

When the peeling test was done with the laminated body obtained in Example 3, peeling did not generate | occur | produce in the whole when it wound 180 degree around each cylindrical rod of diameter 200mm, 160mm, 120mm, 100mm, and 60mm.

The support body B was peeled off, unwinding the laminated body wound up in roll shape in the above, and the laminated body comprised from a transparent resin film and a protective film was wound up. By the method similar to Example 1, the white cloud, a wound | wound, total light transmittance, a yellow index, and the amount of residual solvent of the transparent resin film which peeled the protective film were evaluated. The results are shown in Table 1.

The transparent resin film was introduce | transduced into the drying furnace, and was further dried (this drying), peeling a protective film, unwinding the laminated body roll of the protective film of Example 3 and a transparent resin film. The temperature of the drying furnace was 200 degreeC, the conveyance speed was 1.0 m / min, and the drying time was 12 minutes. The transparent resin film after drying in the drying furnace bonded a protective film (Toray Tech (trademark) 7332K by Toray Film Processing Co., Ltd., polyolefin protective film of weak adhesive force) to one side, and wound up on the roll core. It was 1 mass% when the protective film was peeled off and the amount of residual solvent of the transparent resin film after this drying was measured. The transparent resin film obtained by this drying can also be used as a window film base material.

Example 4

Except using the support B as a support body, it processed like Example 2 and obtained the roll of the laminated body which consists of a PET film which has a protective film, a transparent resin film, and a hard-coat layer.

When the peeling test was done with the laminated body obtained in Example 4, peeling did not generate | occur | produce in the whole when it wound 180 degree around each cylindrical rod of diameter 200mm, 160mm, 120mm, 100mm, and 60mm.

The support body B was peeled off, unwinding the laminated body wound up in roll shape in the above, and the laminated body comprised from a transparent resin film and a protective film was wound up. By the method similar to Example 1, the white cloud, a wound | wound, total light transmittance, a yellow index, and the amount of residual solvent of the transparent resin film which peeled the protective film were evaluated. The results are shown in Table 1.

The transparent resin film was introduce | transduced into the drying furnace and further dried (this drying), peeling a protective film, unwinding the laminated body roll of the protective film of Example 4 and a transparent resin film. The temperature of the drying furnace was 200 degreeC, the conveyance speed was 1.0 m / min, and the drying time was 12 minutes. The transparent resin film after drying in the drying furnace bonded a protective film (Toray Tech (trademark) 7332K by Toray Film Processing Co., Ltd., polyolefin protective film of weak adhesive force) to one side, and wound up on the roll core. It was 0.6 mass% when the protective film was peeled off and the residual solvent amount of the transparent resin film after this drying was measured. The transparent resin film obtained by this drying can also be used as a window film base material.

Example 5

As a support, it was 193 micrometers in thickness (PET 188 micrometer + hard coating layer 5 micrometers), width 900mm, Martens hardness of 380 N / mm <2> of the cast film forming surface side (namely, hard coating layer surface side), and the logarithmic contact angle difference (| BA | A protective film and a transparent resin were treated in the same manner as in Example 1, except that a polyethylene terephthalate (PET) film (support C: base resin = PET, HC treatment oil) having a long hard coating layer having a length of 0.3 ° was used. The roll of the laminated body which consists of a PET film which has a film and a hard coat layer was obtained.

When the peeling test was done with the laminated body obtained in Example 5, peeling did not generate | occur | produce in the whole when it wound 180 degree | times on each cylindrical rod of diameter 200mm, 160mm, 120mm, 100mm, and 60mm.

The support body C was peeled off, unwinding the laminated body wound up in roll shape in the above, and the laminated body comprised from a transparent resin film and a protective film was wound up. By the method similar to Example 1, the white cloud, a wound | wound, total light transmittance, a yellow index, and the amount of residual solvent of the transparent resin film which peeled the protective film were evaluated. The results are shown in Table 1.

The transparent resin film was introduce | transduced into the drying furnace and further dried (this drying), peeling a protective film, unwinding the laminated body roll of the protective film of Example 5 and a transparent resin film. The temperature of the drying furnace was 200 degreeC, the conveyance speed was 1.0 m / min, and the drying time was 12 minutes. The transparent resin film after drying in the drying furnace bonded a protective film (Toray Tech (trademark) 7332K by Toray Film Processing Co., Ltd., polyolefin protective film of weak adhesive force) to one side, and wound up on the roll core. It was 1 mass% when the protective film was peeled off and the amount of residual solvent of the transparent resin film after this drying was measured. The transparent resin film obtained by this drying can also be used as a window film base material.

Example 6

Except using the support body C as a support body, it processed like Example 2 and obtained the roll of the laminated body which consists of a PET film which has a protective film, a transparent resin film, and a hard-coat layer.

When the peeling test was done with the laminated body obtained in Example 6, peeling did not generate | occur | produce in the whole when it wound 180 degree | times on each cylindrical rod of diameter 200mm, 160mm, 120mm, 100mm, and 60mm.

The support body C was peeled off, unwinding the laminated body wound up in roll shape in the above, and the laminated body comprised from a transparent resin film and a protective film was wound up. By the method similar to Example 1, the white cloud, a wound | wound, total light transmittance, a yellow index, and the amount of residual solvent of the transparent resin film which peeled the protective film were evaluated. The results are shown in Table 1.

The transparent resin film was introduce | transduced into the drying furnace and further dried (this drying), peeling a protective film, unwinding the laminated body roll of the protective film of Example 6 and a transparent resin film. The temperature of the drying furnace was 200 degreeC, the conveyance speed was 1.0 m / min, and the drying time was 12 minutes. The transparent resin film after drying in the drying furnace bonded a protective film (Toray Tech (trademark) 7332K by Toray Film Processing Co., Ltd., polyolefin protective film of weak adhesive force) to one side, and wound up on the roll core. It was 0.6 mass% when the protective film was peeled off and the residual solvent amount of the transparent resin film after this drying was measured. The transparent resin film obtained by this drying can also be used as a window film base material.

Example 7

As a support, it is 193 micrometers in thickness (PET 188 micrometer + hard coating layer 5 micrometers), width 900mm, Martens hardness of 340 N / mm <2> of the cast film forming surface side (namely, hard coating layer surface side), and the logarithmic contact angle difference (| BA | A protective film and a transparent resin were treated in the same manner as in Example 1, except that a polyethylene terephthalate (PET) film (support D: base resin = PET, HC treatment oil) having a long hard coating layer having a length of 0.1 ° was used. The roll of the laminated body which consists of a PET film which has a film and a hard coat layer was obtained.

When the peeling test was done with the laminated body obtained in Example 7, the peeling did not generate | occur | produce in the whole when it wound 180 degree | times on each cylindrical rod of diameter 200mm, 160mm, 120mm, 100mm, and 60mm.

The support body D was peeled off, unwinding the laminated body wound up in roll shape in the above, and the laminated body comprised from a transparent resin film and a protective film was wound up. By the method similar to Example 1, the white cloud, a wound | wound, total light transmittance, a yellow index, and the amount of residual solvent of the transparent resin film which peeled the protective film were evaluated. The results are shown in Table 1.

The transparent resin film was introduce | transduced into the drying furnace and further dried (this drying), peeling a protective film, unwinding the laminated body roll of the protective film of Example 7 and a transparent resin film. The temperature of the drying furnace was 200 degreeC, the conveyance speed was 1.0 m / min, and the drying time was 12 minutes. The transparent resin film after drying in the drying furnace bonded a protective film (Toray Tech (trademark) 7332K by Toray Film Processing Co., Ltd., polyolefin protective film of weak adhesive force) to one side, and wound up on the roll core. It was 1 mass% when the protective film was peeled off and the amount of residual solvent of the transparent resin film after this drying was measured. The transparent resin film obtained by this drying can also be used as a window film base material.

Example 8

Except using the support body D as a support body, it processed like Example 2 and obtained the roll of the laminated body which consists of a PET film which has a protective film, a transparent resin film, and a hard-coat layer.

When the peeling test was done with the laminated body obtained in Example 8, peeling did not generate | occur | produce in the whole when it wound 180 degree around each cylindrical rod of diameter 200mm, 160mm, 120mm, 100mm, and 60mm.

The support body D was peeled off, unwinding the laminated body wound up in roll shape in the above, and the laminated body comprised from a transparent resin film and a protective film was wound up. By the method similar to Example 1, the white cloud, a wound | wound, total light transmittance, a yellow index, and the amount of residual solvent of the transparent resin film which peeled the protective film were evaluated. The results are shown in Table 1.

The transparent resin film was introduce | transduced into the drying furnace and further dried (this drying), peeling a protective film, unwinding the laminated body roll of the protective film of Example 8 and a transparent resin film. The temperature of the drying furnace was 200 degreeC, the conveyance speed was 1.0 m / min, and the drying time was 12 minutes. The transparent resin film after drying in the drying furnace bonded a protective film (Toray Tech (trademark) 7332K by Toray Film Processing Co., Ltd., polyolefin protective film of weak adhesive force) to one side, and wound up on the roll core. It was 0.6 mass% when the protective film was peeled off and the residual solvent amount of the transparent resin film after this drying was measured. The transparent resin film obtained by this drying can also be used as a window film base material.

Example 9

As a support, it had a thickness of 193 µm (PET 188 µm + hard coating layer 5 µm), a width of 900 mm, a Martens hardness of 300 N / mm 2 on the cast film forming surface side (that is, a hard coat layer surface side), and a logarithmic contact angle difference (| BA | A protective film and a transparent resin were treated in the same manner as in Example 1, except that a polyethylene terephthalate (PET) film (support E: base resin = PET, HC treatment oil) having a long hard coating layer having a length of 2.7 ° was used. The roll of the laminated body which consists of a PET film which has a film and a hard coat layer was obtained.

When the peeling test was done with the laminated body obtained in Example 9, peeling did not generate | occur | produce in the whole when it wound 180 degree | times on each cylindrical rod of diameter 200mm, 160mm, 120mm, 100mm, and 60mm.

The support body E was peeled off, unwinding the laminated body wound up in roll shape in the above, and the laminated body comprised from a transparent resin film and a protective film was wound up. By the method similar to Example 1, the white cloud, a wound | wound, total light transmittance, a yellow index, and the amount of residual solvent of the transparent resin film which peeled the protective film were evaluated. The results are shown in Table 1.

The transparent resin film was introduce | transduced into the drying furnace and further dried (this drying), peeling a protective film, unwinding the laminated body roll of the protective film of Example 9 and a transparent resin film. The temperature of the drying furnace was 200 degreeC, the conveyance speed was 1.0 m / min, and the drying time was 12 minutes. The transparent resin film after drying in the drying furnace bonded a protective film (Toray Tech (trademark) 7332K by Toray Film Processing Co., Ltd., polyolefin protective film of weak adhesive force) to one side, and wound up on the roll core. It was 1 mass% when the protective film was peeled off and the amount of residual solvent of the transparent resin film after this drying was measured. The transparent resin film obtained by this drying can also be used as a window film base material.

Example 10

Except using the support E as a support body, it processed like Example 2 and obtained the roll of the laminated body which consists of a PET film which has a protective film, a transparent resin film, and a hard-coat layer.

When the peeling test was done with the laminated body obtained in Example 10, peeling did not generate | occur | produce in the whole when it wound 180 degree | times on each cylindrical rod of diameter 200mm, 160mm, 120mm, 100mm, and 60mm.

The support body E was peeled off, unwinding the laminated body wound up in roll shape in the above, and the laminated body comprised from a transparent resin film and a protective film was wound up. By the method similar to Example 1, the white cloud, a wound | wound, total light transmittance, a yellow index, and the amount of residual solvent of the transparent resin film which peeled the protective film were evaluated. The results are shown in Table 1.

The transparent resin film was introduce | transduced into the drying furnace and further dried (this drying), peeling a protective film, unwinding the laminated body roll of the protective film of Example 10 and a transparent resin film. The temperature of the drying furnace was 200 degreeC, the conveyance speed was 1.0 m / min, and the drying time was 12 minutes. The transparent resin film after drying in the drying furnace bonded a protective film (Toray Tech (trademark) 7332K by Toray Film Processing Co., Ltd., polyolefin protective film of weak adhesive force) to one side, and wound up on the roll core. It was 0.6 mass% when the protective film was peeled off and the residual solvent amount of the transparent resin film after this drying was measured. The transparent resin film obtained by this drying can also be used as a window film base material.

Example 11

As a support body, the elongate polyethylene terephthalate (PET) film of thickness 188 micrometers, width 900mm, Martens hardness of 268 N / mm <2> of a cast film forming surface, and logarithmic contact angle difference (| BA |) = 3.1 degree of a cast film forming surface ( A polyimide film was produced in the same manner as in Example 1 except that the support F: base resin = PET and no HC treatment was used, and a roll of a laminate composed of a protective film, a transparent resin film, and a PET film was obtained.

When the peeling test was done with the laminated body obtained in Example 11, peeling did not generate | occur | produce in the whole when it wound 180 degree | times on each cylindrical rod of diameter 200mm, 160mm, 120mm, 100mm, and 60mm.

The support body F was peeled off, unwinding the laminated body wound up in roll shape in the above, and the laminated body comprised from a transparent resin film and a protective film was wound up. By the method similar to Example 1, the white cloud, a wound | wound, total light transmittance, a yellow index, and the amount of residual solvent of the transparent resin film which peeled the protective film were evaluated. The results are shown in Table 1.

The transparent resin film was introduce | transduced into the drying furnace and further dried (this drying), peeling a protective film, unwinding the laminated body roll of the protective film of Example 11 and a transparent resin film. The temperature of the drying furnace was 200 degreeC, the conveyance speed was 1.0 m / min, and the drying time was 12 minutes. The transparent resin film after drying in the drying furnace bonded a protective film (Toray Tech (trademark) 7332K by Toray Film Processing Co., Ltd., polyolefin protective film of weak adhesive force) to one side, and wound up on the roll core. It was 1 mass% when the protective film was peeled off and the amount of residual solvent of the transparent resin film after this drying was measured. The transparent resin film obtained by this drying can also be used as a window film base material.

Example 12

Except using the support body F as a support body, it processed like Example 2 and obtained the roll of the laminated body which consists of a protective film, a transparent resin film, and a PET film.

When the peeling test was done with the laminated body obtained in Example 12, peeling did not generate | occur | produce in the whole when it wound 180 degree | times on each cylindrical rod of diameter 200mm, 160mm, 120mm, 100mm, and 60mm.

The support body F was peeled off, unwinding the laminated body wound up in roll shape in the above, and the laminated body comprised from a transparent resin film and a protective film was wound up. By the method similar to Example 1, the white cloud, a wound | wound, total light transmittance, a yellow index, and the amount of residual solvent of the transparent resin film which peeled the protective film were evaluated. The results are shown in Table 1.

The transparent resin film was introduce | transduced into the drying furnace and further dried (this drying), peeling a protective film, unwinding the laminated body roll of the protective film of Example 12 and a transparent resin film. The temperature of the drying furnace was 200 degreeC, the conveyance speed was 1.0 m / min, and the drying time was 12 minutes. The transparent resin film after drying in the drying furnace bonded the protective film (Toray Tech (trademark) 7332K made from Toray Film Processing Co., Ltd., polyolefin protective film of weak adhesive force) to one side, and wound up on the roll core. It was 0.6 mass% when the protective film was peeled off and the residual solvent amount of the transparent resin film after this drying was measured. The transparent resin film obtained by this drying can also be used as a window film base material.

Comparative Example 1

As a support, it is 193 micrometers in thickness (PET 188 micrometer + hard coating layer 5 micrometers), width 900mm, Martens hardness of 410 N / mm <2> of the cast film forming surface side (that is, hard coating layer surface side), and the logarithmic contact angle difference (| BA | A protective film and a transparent resin were treated in the same manner as in Example 1, except that a polyethylene terephthalate (PET) film (support G: base resin = PET, HC treated oil) having a long hard coating layer of 8.5 ° was used. The roll of the laminated body which consists of a PET film which has a film and a hard coat layer was obtained.

The support body G was peeled off, unwinding the laminated body wound up in roll shape in the above, and the laminated body comprised from a transparent resin film and a protective film was wound up. By the method similar to Example 1, the white cloud, a wound | wound, total light transmittance, a yellow index, and the amount of residual solvent of the transparent resin film which peeled the protective film were evaluated. The results are shown in Table 1.

Comparative Example 2

Except using the support F as a support body, it processed like Example 2 and obtained the roll of the laminated body which consists of a PET film which has a protective film, a transparent resin film, and a hard-coat layer.

The support body G was peeled off, unwinding the laminated body wound up in roll shape in the above, and the laminated body comprised from a transparent resin film and a protective film was wound up. By the method similar to Example 1, the white cloud, a wound | wound, total light transmittance, a yellow index, and the amount of residual solvent of the transparent resin film which peeled the protective film were evaluated. The results are shown in Table 1.

In the above embodiment, the difference (| B-A |) of the logarithmic contact angle before and after washing the support surface with γ-butyrolactone is in a range of 8.0 ° or less, in which case no clouding occurs. On the other hand, in Comparative Examples 1 and 2, the difference (| B-A |) of the logarithmic contact angle before and after washing the support surface with γ-butyrolactone exceeds 8.0 °, and turbidity occurs. The photograph which the turbidity of the comparative example generate | occur | produced is attached as FIG. In FIG. 4, the part which looks white in the whole is white, and the part which is not white shown by the arrow (→) in FIG. 4 is the trace which rubbed with a finger, and it turns out that it disappears when rubbed with a finger.

In the said Example, although the wound was in the guide roll which conveys a support body, presence of a wound was not confirmed on the transparent resin film obtained in Examples 1-10, but wound on the transparent resin film obtained in Examples 11-12. The presence of was confirmed. It is thought that this is because martens hardness of the side on which the transparent resin film of a support body is coated is not more than predetermined value (300 N / mm <2>). The photograph which the wound of Example 11 arose is attached as FIG. The white part between two arrows is a wound, and this wound was 10 mm in length, and it generate | occur | produced on the transparent resin film of Example 11 at the same period as the outer periphery of a guide roll.

[Industry availability]

The laminated body of this invention is used at the time of manufacture of a transparent resin film, is to reduce the defect (cloudiness) at the time of manufacture of a transparent resin film, and a yield is improved and it also leads to the reduction of manufacturing cost.

1: support
2: transparent resin film
3: protective film
10: support roll
11: guide roll
12: coating process
13: predrying process
14: protective film roll
15: 3-layer winding roll

Claims (14)

A laminate in which a support and a transparent resin film are laminated to be peelable, wherein the support is measured after washing the logarithmic contact angle of the laminated surface with the transparent resin film with A, and the laminated surface with γ-butyrolactone and drying. When one logarithmic contact angle is B, | BA | is a laminated body characterized by 8.0 degrees or less. The method of claim 1,
The said support body is a laminated body whose martens hardness of the side which contacts the said transparent resin film is 300 N / mm <2> or more. The method of claim 1,
The laminated body whose said support body is a resin film. The method of claim 1,
The laminated body whose said support body is a resin film which provided the hard-coat layer. The method of claim 1,
The said support body is any one of a polyethylene terephthalate film, a cycloolefin type film, an acryl type film, a polyethylene naphthalate film, a polypropylene film, and a triacetyl cellulose film which has a hard-coat layer. The method of claim 1,
The laminated body whose said transparent resin film is a polyimide-type film. The method of claim 1,
The said laminated resin film is a laminated body whose film thickness is 10-500 micrometers and is a polyimide film which has a haze of 1% or less, a total light transmittance of 85% or more, and a yellow index of 4 or less. The method of claim 1,
The said support body is a laminated body whose arithmetic mean roughness (Ra) prescribed | regulated to JISB0601-2001 of the side which contacts the said transparent resin film is 0.01 micrometer or less. The method of claim 1,
The said support body is a laminated body whose maximum height (Rz) prescribed | regulated to JISB0601-2001 of the side which contacts the said transparent resin film is 0.1 micrometer or less. The laminated body film roll which wound up the laminated body in any one of Claims 1-9. a) The resin varnish obtained by mixing and stirring the resin composition for forming a transparent resin film with a solvent is apply | coated on a support body, and the logarithmic contact angle of the laminated surface of the said support body with the said transparent resin film is A, When the laminated surface is washed with γ-butyrolactone and dried, the logarithmic contact angle measured is set to B, where | BA | is 8.0 ° or less; And
b) removing the solvent by drying the applied resin varnish and forming a layer of a transparent resin film on the support;
The manufacturing method of the laminated body of Claim 1 containing this. delete delete delete

Images