KR102025965B1

KR102025965B1 - Protective film, film layered product and polarizer

Info

Publication number: KR102025965B1
Application number: KR1020150049537A
Authority: KR
Inventors: 치카라 무라타; 마사야스 스즈키; 마사오미 구와바라; 마코토 고토; 마코토 무라타
Original assignee: 가부시키가이샤 도모에가와 세이시쇼
Priority date: 2014-04-08
Filing date: 2015-04-08
Publication date: 2019-09-26
Also published as: CN104977633A; CN104977633B; KR20150116802A

Abstract

[assignment]
It provides a low permeability and a self-supporting protective film in a thin layer state.
[Workaround]
The protective film which concerns on this invention is formed of the repeating unit which has a structure derived from a bifunctional urethane (meth) acrylate, and since the said repeating unit has a several types of saturated cyclic aliphatic group, even if it is a thin layer, it is said The polarizing film which bonded the protective film is hard to absorb a polarizing film even in a high temperature, high humidity environment, and the expansion and contraction of a polarizing film is suppressed.

Description

Protective film, film laminate and polarizing plate {PROTECTIVE FILM, FILM LAYERED PRODUCT AND POLARIZER}

The present invention relates to a protective film, a film laminate and a polarizing plate.

Background Art In recent years, liquid crystal displays used for TVs and mobile devices are becoming thinner, and technology development is progressing with the aim of extremely thin components, particularly polarizers, used in these displays. A polarizing plate generally sticks optical films, such as triacetyl cellulose (henceforth TAC), with an adhesive as a protective film on both surfaces of the polarizing film which consists of a polyvinyl alcohol-type film which adsorbed iodine and uniaxially stretched. It is a combined configuration. In order to bond a TAC film to a polarizing film, a hydrophilic adhesive agent is used.

Such a conventional polarizing plate is due to the high moisture permeability of the TAC film as a protective film, or the expansion and contraction due to moisture absorption and dehumidification. Therefore, when the polarizing plate is left in a high humidity environment, particularly a high temperature and high humidity environment for a long time, the optical function as a polarizing plate is reduced. There was a problem that physical problems are caused by damage or curling, bending of the polarizing plate.

In order to improve these points, the case where the acrylic film or polyester film with low moisture permeability is used is increasing. Moreover, the method of using an energy-beam curable composition as an adhesive agent was also employ | adopted as a method of adhering a protective film to a polarizing film. However, as a method of adhering a protective film to a polarizing film, it is difficult to thin a protective film (for example, 40 micrometers or less) from a viewpoint of the handleability and durability at the time of operation, and it has become a big subject.

In order to solve such a problem, in patent document 1, the uncured ionizing radiation curable resin (energy-ray cured resin) was apply | coated on the base film or the base film in which the mold release layer was formed, and the polarizing film was bonded to this application surface. Then, the method of forming a protective film in a polarizing film by hardening the said cured resin and peeling a base film is proposed.

In addition, Patent Literature 2 discloses a technique for achieving a thin film by forming a functional layer and an adhesive layer on a base film having a release layer formed on both surfaces thereof, and adhering the polarizing film. In addition, patent document 3 describes the method of forming the protective film which protects a polarizing film by the film thickness of 40 micrometers or less by apply | coating and hardening an energy-beam cured resin directly to a polarizing film.

Japanese Patent Laid-Open No. 2006-163082 Japanese Patent Laid-Open No. 2012-27260 Japanese Patent Application Laid-Open No. 2014-010311

However, as the protective film becomes a thin film, moisture tends to permeate easily, so the moisture permeability tends to increase, and the polarizing plate bonded to the protective film tends to be hygroscopic and dehumidified. In addition, when the protective film which does not have independence, ie, which cannot maintain a shape by the protective film itself, is used, the stretching and contraction of the polarizing film due to moisture absorption and desorption cannot be suppressed. As a result, there exists a problem that a crack generate | occur | produces in a polarizing film, or a polarizing film and a protective film peel, and the function of a polarizing plate is not exhibited.

With respect to such a problem, in any of the above-mentioned patent documents, both the protective film and the adhesive energy ray cured film forming the protective film have no detailed description of the moisture permeability, and are said to form an independent protective film with independence. There is no technology, and the above problem cannot be said to be solved.

In view of the above problems, an object of the present invention is to provide a protective film having low water vapor permeability and being self-supporting in a thin layer state.

As a result of diligent studies by the present inventors, the present inventors focused on urethane (meth) acrylate monomers which were hardly conceived as a protective film material in the past, and have urethane (meth) acryl having plural kinds of saturated cyclic aliphatic groups. It was found that the protective film obtained from the rate monomer had low water vapor permeability and had independence in the state of the thin layer.

The following aspects are included in the present invention.

It is formed of the repeating unit which has a structure derived from <1> bifunctional urethane (meth) acrylate,

The said repeating unit has a some kind of saturated cyclic aliphatic group, The protective film characterized by the above-mentioned.

<2> the repeating unit which is block A,

It is comprised by the copolymer containing the block B which consists of a bifunctional (meth) acrylate-derived structure which has one type of saturated cyclic aliphatic group, The protective film as described in <1> characterized by the above-mentioned.

<3> a polymer chain composed of a plurality of repeating units,

The protective film as described in <1> or <2> characterized by the structure which has a thioether bond in the middle of the said polymer chain or the terminal of the said polymer chain at least.

<4> The repeating unit,

The following structure A containing a saturated cyclic aliphatic group R ¹ , and

Saturated cyclic aliphatic groups <1> to the protective film according to any one of <3> characterized in that comprises the structure C including the R ^3.

-CO-NH-R ^1- NH-CO-... (Structure A)

-O-R ^3- O-... (Structure C)

<5> The repeating unit,

Saturated fat protection film according to structure B that includes the shackles R ² to <4> further comprising.

^-O-R 2 -CO- ... (Structure B)

<6> The said repeating unit is a structure represented by following General formula (1), The protective film as described in <5> characterized by the above-mentioned.

[Formula 1]

(In General Formula (1), R ¹ represents a saturated cyclic aliphatic group, R ² represents a saturated aliphatic chain including a linear or branched chain structure having 5 to 10 carbon atoms, and R ³ represents a saturated cyclic aliphatic group different from R ^1. R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom, a methyl group or an ethyl group, m represents an integer of 1 to 4, r and s each represent an integer of 0 to 2, and r The sum of and s is 1 to 2, x represents an integer of 0 to 3)

<7> The said repeating unit is a structure represented by following General formula (2), The protective film as described in <4> characterized by the above-mentioned.

[Formula 2]

(In General Formula (2), R ¹ represents a saturated cyclic aliphatic group, R ² represents a saturated aliphatic chain including a linear or branched chain structure having 5 to 10 carbon atoms, and R ³ represents a saturated cyclic aliphatic group different from R ^1. R <^4> represents a hydrogen atom or a methyl group, R <^5> represents a hydrogen atom, a methyl group, or an ethyl group, m represents the integer of 1-4, k represents the integer of 0-2, n represents 0-2 An integer, x represents an integer of 0 to 3)

<8> The said repeating unit is a structure represented by following General formula (3), The protective film as described in <5> characterized by the above-mentioned.

[Formula 3]

(In General Formula (3), R ¹ represents a saturated cyclic aliphatic group, R ² represents a saturated aliphatic chain including a linear or branched chain structure having 5 to 10 carbon atoms, and R ³ represents a saturated cyclic aliphatic group different from R ^1. R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom, a methyl group or an ethyl group, m represents an integer of 1 to 4, r and s each represent an integer of 0 to 2, and r The sum of and s is 1 to 2, x represents an integer of 0 to 3)

<9> The said repeating unit is a structure represented by following General formula (4), The protective film as described in <4> characterized by the above-mentioned.

[Formula 4]

(In General Formula (4), R ¹ represents a saturated cyclic aliphatic group, R ² represents a saturated aliphatic chain including a linear or branched chain structure having 5 to 10 carbon atoms, and R ³ represents a saturated cyclic aliphatic group different from R ^1. R <^4> represents a hydrogen atom or a methyl group, R <^5> represents a hydrogen atom, a methyl group, or an ethyl group, m represents the integer of 1-4, k represents the integer of 0-2, n represents 0-2 An integer, x represents an integer of 0 to 3)

<10> The protection according to any one of <4> to <9>, wherein R ¹ is a 3-methylene-3,5,5-trimethylcyclohexane ring, and R ³ is a dimethylene tricyclodecane ring. film.

<11> The said block B is a structure represented by following General formula (5), The protective film as described in <2> characterized by the above-mentioned.

[Formula 5]

(In General Formula (5), R ⁶ represents a saturated cyclic aliphatic group, R ⁷ represents a hydrogen atom or a methyl group, and y and z are integers of 0 to 2).

<12> The protective film according to <11>, wherein R ⁶ is a tricyclodecane ring.

<13> The protective film according to <3>, wherein the structure having the thioether bond is a structure represented by the following General Formula (6).

[Formula 6]

(In formula (6), R <^8> represents the C1-C2 alkyl chain whose hydrogen atom may be substituted by the methyl group, X represents each independently -S- or -SH, n is a 1-4 Represents an integer)

<14> The protective film according to <3>, wherein the structure having the thioether bond is a structure represented by the following General Formula (7).

[Formula 7]

(In General formula (7), R <^9> represents the C1-C2 alkyl chain in which a hydrogen atom may be substituted by the alkyl group, X represents each independently -S- or -SH, R <^10> represents a hydrogen atom or Methyl group, p represents an integer of 1 to 3)

<15> while the water vapor transmission rate is 150 g / (m ² · 24 hours) or less,

Moreover, tensile elasticity modulus is 1500 Mpa or more, or tensile strength is 25 Mpa or more, The protective film in any one of <1>-<14> characterized by the above-mentioned.

<16> On at least one side of the protective film of any one of Claims 1-15,

(1) the film base material which supports the said protective film,

(2) a hard coat layer having scratch resistance,

(3) an antiglare layer which scatters light,

(4) The film laminated body provided with any one of the anti-reflection layer comprised from the high refractive index layer provided on the said protective film, and the low refractive index layer provided in the said high refractive index layer.

The polarizing plate provided with the protective film in any one of <1>-<15> on at least one surface of a <17> polarizing film.

Even if the protective film which concerns on this invention is a thin layer, even if it is low moisture permeability, the polarizing film which bonded the said protective film is hard to absorb moisture even in a high temperature, high humidity environment, and expansion and contraction of a polarizing film is suppressed.

Hereinafter, although the protective film, film laminated body, and polarizing plate which concern on this invention are demonstrated, this invention is limited to the following description and is not interpreted.

<< protective film >>

The protective film which concerns on this invention is formed of the repeating unit which has a structure derived from the urethane (meth) acrylate which is a monomer, and the said repeating unit has a several types of saturated cyclic aliphatic group. That is, in the said protective film, the matrix which forms a polymer is formed of the repeating unit which has a structure derived from urethane (meth) acrylate.

The protective film which concerns on this invention is comprised by the said repeating unit at least, and when dividing the basic aspect of a structure into large, (1) the aspect which mainly makes the said repeating unit, (2) let the said repeating unit be a block A, and (3) Structure which mainly has a copolymer with block B, (3) Polymer chain which mainly uses the said repeating unit, or the copolymer of the said block A and block B has a thioether bond (henceforth "thioether structure" suitably. There is a sun including). First, the structure of basic (1) is demonstrated, and it demonstrates in order of (2) and (3).

The protective film which concerns on this invention is formed of the repeating unit which has a structure derived from bifunctional urethane (meth) acrylate, and the said repeating unit has a several types of saturated cyclic aliphatic group. That is, in the said protective film, the matrix which forms a polymer is formed of the repeating unit which has a structure derived from urethane (meth) acrylate.

With the structure derived from the said urethane (meth) acrylate, the double bond of the (meth) acrylate group in a urethane (meth) acrylate monomeric unit, ie, the urethane (meth) acrylate which is a monomer, cleaves. It means one structure, and since it has the site | part which the double bond of the (meth) acrylate group cleaved at both ends, it is bifunctional.

The repeating unit has a urethane bond (-NH-CO-O-). The number of the said urethane bonds is not specifically limited, For example, 1-8. The said urethane bond is a polar group, and the urethane bonds in each repeating unit adjoin by intermolecular force. On the other hand, the saturated cyclic aliphatic group has a nonpolar cyclic structure and has a high molecular weight. It can be considered that the high molecular weight of the saturated cyclic aliphatic group contributes to the intermolecular interaction between the urethane bonds, so that the intermolecular force generates high cohesive force. As a result, the protective film comprised by the said repeating unit is self-supporting, and also has low moisture permeability in the state of a thin layer.

The urethane (meth) acrylate monomer unit has a plurality of saturated cyclic aliphatic groups. Although it does not specifically limit as a saturated cyclic aliphatic group, From a viewpoint of improving the cohesion force resulting from molecular weight, it is preferable that it is a 5-membered ring or more saturated cyclic aliphatic group. Although the upper limit of a ring member is not specifically limited, From the point which is easy to synthesize | combine the monomer used as a raw material of a protective film, it is 15 or less ring, for example, Preferably it is 10 or less ring. When said saturated ring aliphatic group has a plurality of cyclic structures, when a saturated cyclic aliphatic group has the cyclic structure of the largest cyclic structure, when a saturated cyclic aliphatic group has a bicyclo ring or a tricyclo ring, the bridge | bridging bridge | bridging carbon is bridge | crosslinked. It means an annular ring of cyclic structure excluding carbon. For example, in the case of a tricyclodecane ring, the ring number is 9.

The main chain of the cyclic structure of a saturated cyclic aliphatic group may be formed only by the carbon atom, and may be formed by the oxygen atom and / or the nitrogen atom in addition to a carbon atom. In addition, a C1-C10 linear and / or branched structure may be added to the carbon atom of the said cyclic structure.

As an example of the said saturated cyclic aliphatic group, a 3,5, 5- trimethyl cyclohexane ring, a tricyclodecane ring, an adamantane ring, etc. are mentioned. The said saturated cyclic aliphatic group may be couple | bonded with the urethane bond group through the saturated aliphatic chain, and the rigidity of a repeating unit can be suitably adjusted by changing the carbon number of a saturated aliphatic chain. Examples of the saturated aliphatic chain include a straight chain structure and a branched chain structure, and examples of the straight chain structure include-(CH ₂ ) _n- (n is an integer of 1 to 10). in view to increase, in particular, - (CH ₂₎ - or - (CH _{2) 2} - is preferably a. On the other hand, as a branched structure, the structure by which at least 1 hydrogen on carbon of the said linear structure was substituted by the methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc. is illustrated.

When the 3,5,5-trimethylcyclohexane ring described above is bonded to two urethane bonds through a methylene chain, the 3-methylene-3,5,5-trimethylcyclohexane ring is bonded to each urethane bond, When the tricyclodecane ring is bonded to two urethane bonds through a methylene chain, the dimethylene tricyclodecane ring is bonded to each urethane bond.

Said 3-methylene-3,5,5-trimethylcyclohexane ring and a dimethylene tricyclodecane ring are preferable ring structures, and in the protective film which contains the said ring structure in a polymer chain, low moisture permeability and independence are represented suitably. do.

It is preferable that the C5-C10 saturated aliphatic chain is contained in the main chain of a repeating unit other than a saturated cyclic aliphatic group. By having 5 or more carbon atoms in a saturated aliphatic chain, a chain length is long and flexibility is provided to a repeating unit by the saturated aliphatic chain which has flexibility, and brittleness of a protective film is reduced. On the other hand, when carbon number is 10 or less, increase in the water vapor transmission rate in a protective film can be suppressed. The saturated aliphatic chain may have a straight chain structure or a branched chain structure. The said saturated aliphatic chain comprises a part of repeating unit as a structure through a urethane bond or ester bond, for example.

An example of the straight chain structure, - (CH ₂₎ _n1 - can be of the (n1 is an integer of 5-10), in particular, - (CH ₂₎ ₅ - is preferably. On the other hand, as a branched structure, the structure by which at least 1 hydrogen on carbon of the said linear structure was substituted by the methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc. is illustrated.

As an example of the repeating unit it can be given a structure that includes the following structure C that includes the following structure A, and a saturated cyclic aliphatic group R ³ containing a saturated cyclic aliphatic group R ^1.

-CO-NH-R ^1- NH-CO-... (Structure A)

-O-R ^3- O-... (Structure C)

The said repeating unit can be obtained from the urethane (meth) acrylate obtained using the diisocyanate containing R <^1> , the diol containing R <^3> , and (meth) acrylate, for example, and can manufacture it easily. As an example, the ratio of the said structure A and the structure C can be m + 1: m or m: m + 1, and said m represents the integer of 1-4.

Further, the repeating units, to further may include the following structure B containing saturated fat shackles R ^2.

^-O-R 2 -CO- ... (Structure B)

The said repeating unit has a (meth) acrylate or a (meth) acryl group in addition to the diisocyanate containing R <^1> , the ester containing R <^2> (it is used arbitrarily), and the diol containing R <^3>, for example. It can obtain using isocyanate and can manufacture easily. As an example, the ratio of the structure A, the structure B, and the structure C is m + 1: m (r + s): m, m + 1: k + n: m, m: m (r + s): m + 1 , m: k + n: m + 1. M represents an integer of 1 to 4, r and s each represent an integer of 0 to 2, and a sum of r and s is 1 to 2, k represents an integer of 0 to 2, and n represents 0 It represents the integer of -2.

The specific example of the repeating unit which has the saturated cyclic aliphatic group and saturated aliphatic chain mentioned above is shown below. As it is shown in formula (1), a (meth) acrylate of the structure is derived from a (meth) acrylate structure _{H 2 C = CH-CO 2} - ( _{or, H 2 C = C (CH} 3) -CO 2 Carbon-carbon double bond of-) cleaves and becomes single bond.

[Formula 8]

By making m in the said General formula (1) be an integer of 1-4, the water vapor transmission rate of a protective film can be reduced more, and tensile elasticity modulus and tensile strength can be raised further. It is more preferable that m is 1 or 2, More preferably, it is 1. The same applies to the general formulas (2), (3), and (4) described later.

In the general formula (1), R ¹ is a 3-methylene-3,5,5-trimethylcyclohexane ring, R ² is-(CH ₂ ) _5- , and R ³ is a dimethylene tricyclodecane ring and, R ⁴ and R ⁵ is a hydrogen atom, r and s are the 1, x represents a first preferred structure of the following.

[Formula 9]

Other specific examples of the repeating unit are shown below.

[Formula 10]

In the general formula (2), R ¹ is a 3-methylene-3,5,5-trimethylcyclohexane ring, R ² is-(CH ₂ ) _5- , and R ³ is a dimethylene tricyclodecane ring And the preferable repeating unit whose R <^4> and R <^5> is a hydrogen atom and k and n are 1 are shown below.

[Formula 11]

Moreover, the specific example of a repeating unit is shown below.

[Formula 12]

In the general formula (3), R ¹ is 3-methylene and -3,5,5- trimethyl cyclohexane ring, R ² is - (CH ₂₎ ₅ -, and, R ³ is dimethyl rental Lee cyclo decane ring, and , R ⁴ and R ⁵ are hydrogen atoms, r and s are 1, and a preferable repeating unit in which x is 1 is shown below.

[Formula 13]

Other specific examples of the repeating unit are shown below.

[Formula 14]

In the general formula (4), R ¹ is a 3-methylene-3,5,5-trimethylcyclohexane ring, R ² is-(CH ₂ ) _5- , and R ³ is a dimethylene tricyclodecane ring And the preferable repeating unit whose R <^4> and R <^5> is a hydrogen atom and k and n are 1 are shown below.

[Formula 15]

Moreover, the isomer of the structure shown by the said General formula (1a), General formula (2a), General formula (3a), and General formula (4a) is also contained in the repeating unit which concerns on this invention.

Next, the aspect regarding a copolymer in the protective film of this invention is demonstrated. The protective film which concerns on this form is comprised by the copolymer containing the block B which consists of a structure derived from the bifunctional (meth) acrylate which has the said repeating unit which is block A, and one type of saturated cyclic aliphatic group, have. In other words, the protective film which concerns on a copolymer has block A (repeat unit) which consists of a bifunctional urethane (meth) acrylate monomeric unit which has a plurality of saturated cyclic aliphatic group, and one type of saturated cyclic aliphatic group It can be said that it consists of the copolymer containing the block B which consists of a bifunctional (meth) acrylate monomeric unit.

The repeating unit which is the block A is as described above. Block B comprises the bifunctional (meth) acrylate monomer unit which has one type of saturated cyclic aliphatic group. This block B contains a (meth) acrylate monomer unit and does not contain a urethane bond. The site | part derived from the acrylate of block A is couple | bonded with the site | part derived from the acrylate of other block A or block B (-block A-block A- or -block A-block B-).

-CO-O- of the (meth) acrylate moiety in the block B is more linear and lower in flexibility than -CO-NH- which is a nonlinear structure of the urethane (meth) acrylate moiety. In addition, since block B has only one type of saturated cyclic aliphatic group, it has a linear structure than block A, and has high rigidity. The protective film containing the copolymer containing only block A has low moisture permeability and has independence even in the state of a thin layer, but by using block B having high rigidity, the self-supporting property can be further increased to suppress the stretching of the polarizing film due to moisture absorption and dehumidification. Can provide a protective film.

The bifunctional (meth) acrylate monomer unit according to the block B has one type of saturated cyclic aliphatic group. Although it does not specifically limit as a saturated cyclic aliphatic group, It is preferable that it is a 5-membered ring or more saturated cyclic aliphatic group from a viewpoint of obtaining the fall effect of the water vapor transmission rate resulting from molecular weight. Although the upper limit of a ring member is not specifically limited, From the ease of the synthesis | combination of the monomer used as a raw material of block B, it is 15 or less ring, for example, Preferably it is 10 or less ring. When the said saturated ring aliphatic group has a some cyclic structure, when the saturated cycloaliphatic group has a plurality of cyclic structures, it should be taken as showing the ring number of the largest cyclic structure, and when a saturated cyclic aliphatic group has a bicyclo ring or a tricyclo ring, it connects bridgehead carbon. It means a ring of cyclic structure excluding carbon of the bridge. For example, in the case of a tricyclodecane ring, the ring number is 9.

Examples of the saturated cyclic aliphatic group include tricyclodecane ring, 3,5,5-trimethylcyclohexane ring, adamantane ring, and the like. The said saturated cyclic aliphatic group may be couple | bonded through the structure and the saturated aliphatic chain derived from (meth) acrylate, and the rigidity of a repeating unit can be adjusted suitably by changing carbon number of a saturated aliphatic chain. Examples of the saturated aliphatic chain include a straight chain structure and a branched chain structure, and examples of the straight chain structure include-(CH ₂ ) _n- (n is an integer of 1 to 10). in view to increase, in particular, - (CH ₂₎ - or - (CH _{2) 2} - is preferably a. Also, in the case of the structure in which the block B does not have a linear structure, the rigidity is increased (wherein n is 0). On the other hand, as a branched structure, the structure by which at least 1 hydrogen on carbon of the said linear structure was substituted by methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc. is illustrated.

When the above-mentioned 3,5,5-trimethylcyclohexane ring couple | bonds with the structure derived from two (meth) acrylates through a methylene chain, a 3-methylene-3,5,5-trimethylcyclohexane ring is each (meth) When the tricyclodecane ring is bonded to the structure derived from two (meth) acrylates through a methylene chain, the dimethylene tricyclodecane ring is derived from each (meth) acrylate. It is combined with the structure.

The said dimethylene tricyclodecane ring is a preferable ring structure, and low moisture permeability and independence are expressed suitably in the protective film which contains the said ring structure in a polymer chain.

The specific example of the block B which has the saturated cyclic aliphatic group and saturated aliphatic chain mentioned above is shown below. Block B has a structure derived from (meth) acrylate at both terminals, and the structure derived from (meth) acrylate is bonded with another block B or block A (-block B-block B- or -block). B-block A-). As shown in formula (5), parts of the acrylate-derived refers to acrylate structure H ₂ C = HC-CO ₂ - carbon-to carbon double bond cleavage is a combination of the first structure (methacrylate The same is true of the structure).

[Formula 16]

In said general formula (5), R <^6> is a tricyclodecane ring, R <^7> is a hydrogen atom, and the preferable structure whose y and z are 1 is shown below.

[Formula 17]

Although the weight ratio of block A and block B in a copolymer is not specifically limited, The grade of the tensile elasticity modulus of the protective film resulting from block B should be made preferable, and block A: block B = 70: 30-15: 85 It is preferable that it is, It is more preferable that it is 60: 40-15: 85, It is especially preferable that it is 50: 50-15: 85.

Moreover, it is preferable that the ratio of the copolymer in the protective film which concerns on this invention is high from a viewpoint of reducing the water vapor transmission rate of a protective film, and increasing independence, and it is preferable that they are 70 weight% or more and 99.5 weight% or less with respect to the total weight of a protective film. And it is more preferable that they are 80 weight% or more and 99.5 weight% or less.

Next, the thioether structure is demonstrated. The thioether structure has a thioether bond and has at least -S-R structure (R is a hydrocarbon). R of the thioether structure and the reverse side single bond couple | bond with the structure derived from the (meth) acrylate of a repeating unit, and a hydrogen bond arises between -S- of a thioether bond and a urethane bond in a repeating unit, and is protected. Independence of the film can be improved.

A thioether structure should just have at least 1 or more thioether bond (-S-), but it is preferable because including a some thioether bond produces strong hydrogen bond and the independence of a protective film becomes higher.

The hydrocarbon R having a thioether structure has a cyclic structure and / or a chain structure. The main chain of the said cyclic structure and linear structure may be formed only by the carbon atom, and may be formed by the oxygen atom and / or the nitrogen atom in addition to a carbon atom. As the cyclic structure, for example, 1,2,3-triazine ring, 1,2,4-triazine ring, 1,3,5-triazine ring, maleimide ring and the like are exemplified, and as a chain structure,-(CH ₂₎ ) _n2 - may be mentioned the alkyl chain represented by (n2 is an integer of 1-10). The hydrogen atom bonded to the carbon atom and / or nitrogen atom constituting the main chain of the cyclic structure and the chain structure may be substituted with a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or the like.

In addition, the thioether structure may have a substituent, for example, a carbonyl group, a carboxyl group, an amino group, an amide group, and a hydroxyl group are illustrated.

The said thioether structure is couple | bonded with the middle of the polymer chain comprised by (1) some repeating unit, or (2) the terminal of the said polymer chain. In the case of (1), the thioether structure has a plurality of thioether bonds, one thioether bond is bonded to the (meth) acrylate-derived structure of the repeating unit, and another thioether bond is a It is bonded to the structure derived from (meth) acrylate. The bonding state of (1) when a repeating unit has a site | part derived from an acrylate is shown below. Moreover, also when a thioether structure has 3, 4 or more -S-, it couple | bonds with some repeating unit.

[Formula 18]

On the other hand, in the case of (2), the thioether structure is couple | bonded with the terminal of a polymer chain, and the thioether structure is couple | bonded with one repeating unit. The bonding state of (2) in the case where a repeating unit has a site | part derived from an acrylate is shown below.

[Formula 19]

R represents a hydrocarbon.

Although the bonding state of the said repeating unit and the thioether structure was mentioned above, when a polymer chain is formed from the repeating unit (block A) and block B, the (1 ') thioether structure couple | bonds with block A and block B, It may be present, it may be combined with the block A and the other block A, and may be combined with the block B and the other block B. In addition, the (2 ') thioether structure is bonded to block A, and may not be bonded to another block A or block B, and may be bonded to block B and not to block A or other block B.

Although the thioether structure which has one or more thioether bond was mentioned above, the specific example of the thioether structure which has both such a cyclic structure and a chain structure is shown below.

[Formula 20]

The formula (6) of, specific examples of R ⁸ _{example, - (CH 2) -,} - (CH 2) 2 - can be mentioned a and a hydrogen atom of the alkyl chain, a substituent such as a methyl group, an ethyl group, a propyl group It may be substituted by.

X is -S- or -SH, and the structure where two X is -S- is represented by following General formula (6a), One X is -S-, and the other X is -SH, The structure is It is represented by General formula (6b), and the structure whose two X is -SH is represented by the following General formula (6c). -S- of a thioether structure is couple | bonded with the structure derived from the (meth) acrylate of a repeating unit.

[Formula 21]

Moreover, the specific example of the thioether structure which has a chain structure is shown below.

[Formula 22]

The general formula (7), specific examples of R ⁹ _{example, - (CH 2) -,} - (CH 2) 2 - can be mentioned an alkyl chain of which a hydrogen atom of the alkyl chain, a methyl group, an ethyl group, a propyl group It may be substituted by substituents, such as these.

In the general formula (7), among the structures where p is 3, the structure where three X is -S- is represented by the following general formula (7a), two X is -S- and another X is The structure of -SH is represented by the following general formula (7b), one X is -S-, and the structure of two other X is -SH is represented by the following general formula (7c), and three X is The structure which is -SH is represented by the following general formula (7d). -S- of a thioether structure is couple | bonded with the structure derived from the (meth) acrylate of a repeating unit.

[Formula 23]

In particular, since the thioether structure shown by the said General formula (7d) is tetrafunctional, and forms a repeating unit and a complex three-dimensional structure, the protective film obtained has high tensile strength and can improve independence more.

Although the weight ratio of the said repeating unit and thioether structure in a protective film is not specifically limited, The value of the tensile strength of the protective film resulting from a thioether structure should be made preferable, and a repeating unit: thioether structure = 95: 5 It is preferable that it is-50:50, It is more preferable that it is 95: 5-80:20, It is especially preferable that it is 90:10-70:30.

In addition, when a protective film is comprised by the copolymer, the weight ratio of the total amount of a repeating unit (block A) and block B, and a thioether structure is the total amount of a repeating unit (block A) and a block B: thioether structure. It is preferable that it is: 5-50: 50, It is more preferable that it is 95: 5 ~ 80: 20, It is especially preferable that it is 90: 10-70: 30.

Moreover, it is preferable that the ratio of the polymer chain (total ratio of a repeating unit (block A), a block B, and a thioether structure) in the protective film which concerns on this invention is high from a viewpoint of reducing the moisture permeability of a protective film and improving independence, It is preferable that they are 70 weight% or more and 99.5 weight% or less with respect to the total weight of a protective film, and it is more preferable that they are 80 weight% or more and 99.5 weight% or less.

It is judged by analyzing a protective film by pyrolysis GC-MS and FT-IR whether the protective film which concerns on this invention is formed of the polymer chain of a structure (repeating unit (block A), a block B, and a thioether structure). It is possible. In particular, pyrolysis GC-MS is useful because the monomer unit contained in the protective film can be detected as the monomer component.

A protective film may contain various additives, such as a ultraviolet absorber, a leveling agent, an antistatic agent, as long as it does not impair film-forming property, tensile elasticity modulus, tensile strength, and low moisture permeability of a protective film. Thereby, it is possible to provide a ultraviolet ray absorption characteristic, peeling characteristic, and antistatic characteristic to a protective film.

As a ultraviolet absorber, a well-known thing can be used, For example, benzophenone series, such as 2-hydroxy-4- octoxy benzophenone and 2-hydroxy-4- methoxy-5- sulfobenzophenone, 2- ( Hindered amine systems, such as benzotriazole system, such as 2'-hydroxy-5-methylphenyl) benzotriazole, phenyl salicylate, and pt-butylphenyl salicylate, etc. are mentioned. Known ones can also be used for the leveling agent and the antistatic agent.

Since the protective film which concerns on this invention is formed from a thin film, the upper limit of a film thickness is 50 micrometers, for example, More preferably, it is 30 micrometers. Although a lower limit is not specifically limited, From a viewpoint which ensures low moisture permeability reliably, it is preferable that it is 5 micrometers, and it is more preferable that it is 10 micrometers.

The moisture permeability of the protective film according to the present invention may be a low value, 150g / (m ² · 24 hour) or less is preferred, more preferably from 120g / (m ² · 24 hours) or less in the state of a thin layer 30㎛ It is especially preferably 100 g / (m ² · 24 hour) or less. Although the lower limit of water vapor transmission rate is not specifically limited, For example, it is 15 g / (m <^2> * 24) or more.

The protective film according to the present invention has independence. Having independence means that a protective film can hold | maintain a shape by itself, and as a criterion, when a tensile elasticity modulus of a protective film is 1500 Mpa or more, a protective film shall have independence. In order to suppress expansion and contraction of the polarizing film resulting from moisture absorption and dehumidification, it is preferable that tensile elasticity modulus is high, Specifically, it is 1500 Mpa or more, More preferably, it is 2500 Mpa or more. The upper limit is not particularly limited, but is, for example, 4500 MPa.

In addition, as another judgment standard, if the tensile strength of a protective film is 15 Mpa or more, a protective film shall have independence. In order to suppress the expansion and contraction of the polarizing film resulting from moisture absorption and dehumidification, it is preferable that tensile strength is high, More preferably, it is 25 MPa or more. Although an upper limit is not specifically limited, For example, it is 100 MPa.

<< film laminated body >>

Next, a film laminated body is demonstrated. The film laminate according to the present invention, on at least one side of the protective film,

(1) the film base material which supports the said protective film,

(2) a hard coat layer having scratch resistance,

(3) an antiglare layer for scattering light,

(4) Either a high refractive index layer provided on the said protective film, and the anti-reflection layer comprised from the low refractive index layer provided in the said high refractive index layer is provided. Of course, the said film laminated body may be equipped with arbitrary said (1)-(4) on both surfaces of a protective film. That is, on both sides, the same layer (for example, (1) on the surface of the protective film (1) on the back surface) or a heterogeneous layer (for example, (1) on the surface of the protective film (2) on the back surface) Or you may be provided with (2) on the surface and (3)) on the back surface. Moreover, the layer of other (1)-(4) is provided in (1)-(4), and a laminated structure may be sufficient as it. Hereinafter, (1)-(4) is demonstrated.

[Film base material]

The protective film which concerns on this invention can be handled integrally in the state laminated | stacked with the other film. Moreover, when manufacturing a film laminated body by forming a protective film on a film base material by coating methods, such as a roll coating method and the gravure coating method, a film base material can also be used as a part of a film laminated body as it is.

Since a film base material plays a role of supporting a protective film and finally peels off and removes, it is preferable to have a release layer in the side which laminates a protective film. In addition, when a film base material is equipped with a functional layer through a release layer, after bonding a film base material to the functional layer side of a protective film, and peeling and removing a film base material, a functional layer will not normally remain on the film base material side. Is transferred to the protective film side.

Usually, since a protective film and a polarizing film are bonded together by an ultraviolet curable adhesive, it is preferable that a film base material does not have an ultraviolet absorbing ability so that a film base material may not interfere with ultraviolet irradiation. In addition, optical properties may be inspected in various manufacturing processes in which other films are provided on the polarizing plate and processed to the display device, and the influence of the polarizing film and the protective film, which are the basic components of the polarizing plate, to the optical property measurement is minimized. In order to do so, it is preferable that a film base material has transparency. From this viewpoint, the polyester film base material which has a release layer as a film base material is used preferably.

As mentioned above, the said polyester film base material may have a mold release layer, and other functional layers may be further formed other than a mold release layer. Examples of the functional layer include a hard coat layer (HC layer), an antiglare layer (AG layer), and an antireflection layer (LR layer). These layers are formed on the release layer of a polyester film, are laminated | stacked on a protective film, and the film laminated body in which each functional layer and the protective film were laminated | stacked easily is obtained by peeling a polyester base material from a release layer.

[Hard coat layer]

The hard coat layer has hard coat property. The hard coat property in this invention is based on JIS K5600: 1999, and the scratch hardness by the pencil method under the conditions of 500 g of loads and a speed of 1 mm / s is 2H or more.

As the resin component constituting the hard coat layer, since the ionizing radiation curable resin can be cured efficiently by a simple and easy processing operation, it is very suitable, and after the curing, an ionizing radiation curing type that gives a film having sufficient strength and transparency. Resin can be used without particular limitation.

As ionizing radiation curable resin, it has radical polymerizable functional groups, such as acryloyl group, methacryloyl group, acryloyloxy group, and methacryloyloxy group, and cationically polymerizable functional groups, such as an epoxy group, a vinyl ether group, and an oxetane group. A composition in which monomers, oligomers, prepolymers, and polymers are singly or appropriately mixed is used. Examples of the monomer include methyl acrylate, methyl methacrylate, methoxy polyethylene methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, ethylene glycol dimethacrylate, dipentaerythritol hexaacrylate, trimethylolpropane tri Methacrylate, pentaerythritol triacrylate, and the like. As oligomers and prepolymers, acrylate compounds such as polyester acrylate, polyurethane acrylate, polyfunctional urethane acrylate, epoxy acrylate, polyether acrylate, alkyd acrylate, melamine acrylate, silicone acrylate, unsaturated polyester Epoxy compounds such as tetramethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A diglycidyl ether, and various alicyclic epoxy, 3-ethyl-3 Hydroxymethyl oxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di [1-ethyl (3-oxetanyl)] methyl ether Cetane compound is mentioned. Examples of the polymer include polyacrylates, polyurethane acrylates, polyester acrylates, and the like. These can be used individually or in mixture of two or more. Among these ionizing radiation curable resins, in particular, the polyfunctional monomer having three or more functional groups can increase the curing rate or improve the hardness of the cured product. Moreover, hardness, flexibility, etc. of hardened | cured material can be provided by using polyfunctional urethane acrylate.

Although the ionizing radiation curable resin can be cured by ionizing radiation irradiation as it is, in the case of curing by ultraviolet irradiation, addition of a photopolymerization initiator is required. As a photoinitiator, cationic polymerization, such as an acetphenone series, a benzophenone series, a thioxanthone series, benzoin, benzoin methyl ether, such as radical polymerization initiators, an aromatic cyazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, and a metallocene compound The initiators can be used alone or in combination as appropriate.

Although the film thickness of a hard coat layer will not be restrict | limited especially if hard coat property is exhibited, Usually, they are 2 micrometers or more and 10 micrometers or less.

In order to provide functions other than hard coat property, various additives can be added to the said hard coat layer. For example, an electron-conjugated system, a metal oxide system, or a fluorine-based or silicon-based leveling agent added to improve releasability when peeling from a polyester film substrate, or to prevent dust adhesion due to peeling charging at the time of peeling. You may select and use an ionic antistatic agent suitably according to the function required. The point which can use an additive is the same also about the following anti-glare layer and low refractive index layer.

[Antiglare layer]

The anti-glare layer has an anti-glare function for scattering light, and realizes the anti-glare function by external haze and / or internal haze, and the anti-glare layer has irregularities formed on the surface, or contains translucent fine particles therein. Both are.

Although there is no restriction | limiting in particular as a method of forming the unevenness | corrugation of the surface of an anti-glare layer, The method of apply | coating ionizing radiation curable resin on the polyester film base material with an unevenness | corrugation, and hardening after application | coating is easy to control the shape of unevenness | corrugation. Preferred at

The shape of the surface unevenness | corrugation on the polyester base material side of an anti-glare layer is determined according to the anti-glare property calculated | required. The more preferable shape of the unevenness can be defined by the roughness coefficient Ra, more preferably Ra: 0.01 µm or more, Sm: 50 µm to 500 µm, and an average inclination angle of 0.1 ° to 3.0 °.

Although there is no restriction | limiting in particular about the thickness of an anti-glare layer, If it is too thin, the shape of the unevenness | corrugation formed in the support body side will remain also in the unevenness | corrugation formed in the carrier side, and it is unpreferable in glare prevention. On the other hand, when it is too thick, since the curl and the crack generate | occur | produce by hardening shrinkage of resin generate | occur | produce, it is preferable that it is the range of 1-12 micrometers because it is not preferable from the point of handling.

On the other hand, as the light-transmitting fine particles added in the ionizing radiation curable resin to cause internal haze, for example, acrylic resin, polystyrene resin, styrene-acryl copolymer, nylon resin, silicone resin, melamine resin, polyether sulfone resin, and the like. Inorganic fine particles such as organic resin fine particles and silica can be used. Here, it is very suitable that the refractive index difference with a resin component is 0.04 or less, and, as for translucent microparticles | fine-particles, it is more preferable that it is 0.01 or less. A large difference in refractive index with the resin component is not preferable because internal scattering occurs in the antiglare layer and contrast decreases.

The film thickness of the antiglare layer is not particularly limited as long as the antiglare property is exhibited, but is generally 2 μm or more and 10 μm or less. Moreover, the said anti-glare layer can also have hard coat property in addition to anti-glare property, In this case, hard coat property is provided by adjusting the resin component to be used.

Antireflection layer

The antireflection layer is composed of a low refractive index layer and a high refractive index layer. The low refractive index layer is a layer having a lower refractive index than the adjacent high refractive index layer (hard coat layer, antiglare layer or protective film), and contributes to preventing reflection of light on the low refractive index layer side in a state of being laminated with the high refractive index layer. In addition, high refractive index and low refractive index here do not prescribe absolute refractive index, but rather it is prescribed | regulated that it is high or low by comparatively comparing the refractive index of two layers, and when both have relationship of following formula (1) It is considered that reflectance becomes low.

… (Eq. 1)

(n1 is the refractive index of the high refractive index layer, n2 is the refractive index of the low refractive index layer)

In order to exhibit the antireflection function very suitably, the refractive index of the low refractive index layer is preferably 1.45 or less. Examples of the material having these characteristics include LiF (refractive index n = 1.4), MgF ₂ (n = 1.4), 3NaFAlF ₃ (n = 1.4), AlF ₃ (n = 1.4), Na ₃ AlF ₆ (n = 1.33) and the like, and organic low reflection materials such as inorganic low reflection materials contained in acrylic resins, epoxy resins, and the like, fluorine-based, silicon-based organic compounds, thermoplastic resins, thermosetting resins, and radiation-curable resins. Can be mentioned. Especially, since a fluorine-containing fluorine-containing material is excellent in antifouling property, it is preferable at the point of the contamination prevention when a low refractive index layer becomes a surface.

Examples of the fluorine-containing material include vinylidene fluoride copolymers, fluorine-olefin / hydrocarbon copolymers, fluorine-containing epoxy resins, fluorine-containing epoxy acrylates, fluorine-containing silicones, and fluorine-containing alkoxy, which are dissolved in an organic solvent and are easy to handle. Silane, fluorine-containing polysiloxane, and the like. These can also be used individually or in combination of two or more. The fluorine-containing polysiloxane is obtained by curing a hydrolyzable silane compound and / or a mixture containing at least a hydrolyzate thereof and a curing accelerator, and containing a cationic modified silane compound having a function as a film forming agent and an antistatic agent as a hydrolyzable silane compound. It may be.

The film thickness of the low refractive index layer is not particularly limited as long as the antireflection function is exhibited in relation to the high refractive index layer. However, the film thickness of the high refractive index layer is generally 0.05 µm or more and 0.2 µm or less. It is preferable that it is 10 micrometers or less. The low refractive index layer exhibits an antireflection function in relation to the high refractive index layer. However, the low refractive index layer may have a hard coat property by selecting a raw material. In addition, the high refractive index layer may have hard coat property by raw material selection, and may be further equipped with anti-glare property.

<< polarizing plate >>

Next, the polarizing plate provided with the protective film of this invention is demonstrated. The polarizing plate which concerns on this invention is equipped with the said protective film in at least one surface of a polarizing film.

The polarizing film is made of polyvinyl alcohol-based resin (PVA resin), and has a property of transmitting light having a vibrating surface in any direction among light incident on the polarizing film, and absorbing light having a vibrating surface perpendicular to the polarizing film. It is a film and the dichroic dye is typically oriented by adsorption to PVA resin. PVA resin which comprises a polarizing film can be obtained by saponifying polyvinyl acetate type resin. The polyvinyl acetate type resin which becomes a raw material of PVA resin may be a copolymer with vinyl acetate and the other monomer copolymerizable with this besides polyvinyl acetate which is a homopolymer of vinyl acetate. A polarizing film can be manufactured by subjecting the film | membrane which consists of said PVA resin to uniaxial stretching, dyeing with a dichroic dye, and boric acid crosslinking process after dyeing. As a dichroic dye, iodine or a dichroic organic dye is used. Uniaxial stretching may be performed before dyeing with a dichroic dye, may be performed simultaneously with dyeing with a dichroic dye, or after dyeing with a dichroic dye, for example, during boric acid crosslinking treatment. Thus, the polarizing film which consists of PVA resin which is manufactured and the dichroic dye adsorbs and orients becomes one of the constituent materials of a polarizing plate.

Preferably, an ultraviolet curable adhesive agent is used for bonding of a polarizing film and a protective film. As long as UV cure adhesive is supplied in the state which can be applied in a liquid form, well-known thing conventionally used for manufacture of a polarizing plate can be used, From a viewpoint of weather resistance, polymerizability, etc., a cationically polymerizable compound, for example, It is preferable to contain an epoxy compound as one of an ultraviolet curable component.

In addition to the cationically polymerizable compound which makes an epoxy compound the representative example, an ultraviolet curable adhesive agent produces | generates a cationic species or Lewis acid by irradiation of a polymerization initiator, especially an ultraviolet-ray, and the photocationic polymerization initiator for initiating superposition | polymerization of a cationically polymerizable compound. Is formulated. Moreover, you may mix | blend various additives, such as the thermal cationic polymerization initiator which starts superposition | polymerization by heating, and other photosensitizers.

The polarizing plate which concerns on this invention is equipped with the said protective film in at least one surface, and the structure provided with the protective film in both surfaces of a polarizing plate is contained. Since the said protective film is low moisture permeability even if it is a thin layer, even if it is a high temperature, high humidity environment, a polarizing film is hard to absorb moisture, and the expansion and contraction of a polarizing film is suppressed.

<< manufacturing method of protective film and film laminated body >>

[Protective Film Forming Step]

Although the manufacturing method of the protective film which concerns on this invention is not specifically limited if the said protective film can be manufactured, As an example, the method including the protective film formation process containing the following process (A1) and (A2) is mentioned. have.

Process (A1): An energy-beam curable composition is apply | coated on the film base material or the release layer of a film base material.

Step (A2): After application, the energy ray curable composition is cured to form a protective film.

The energy ray curable composition contains urethane (meth) acrylate as an essential component. The said urethane (meth) acrylate which is a monomer is a raw material of a protective film, and the repeating unit mentioned in the said << protective film >> is formed by superposing | polymerizing the said monomer.

In another embodiment, the energy ray curable composition as a raw material of the protective film contains a urethane (meth) acrylate for forming the repeating unit (block A) and a (meth) acrylate for making block B. The copolymer mentioned in the said << protective film >> is formed by copolymerization of these monomers.

Moreover, in another embodiment, the said energy-beam curable composition is a (meth) acrylate and / or thioether structure which makes block B in addition to the urethane (meth) acrylate which produces (block A) which makes the said repeating unit. It contains a thiol to produce. When urethane (meth) acrylates superpose | polymerize or a urethane (meth) acrylate and a (meth) acrylate copolymerize to form a polymer chain, a thiol couple | bonds with the intermediate | middle of a polymer chain or the terminal of a polymer chain, and said << protective film >> A protective film comprising the polymer chain mentioned in the above is formed.

Although the said urethane (meth) acrylate differs from the said repeating unit in that the structure derived from the (meth) acrylate of both terminals is a (meth) acrylate group, the monomer has a several type or one type of saturated cyclic aliphatic group The structure other than both terminals is common, and the same also applies to (meth) acrylate. Specific examples, such as a saturated cyclic aliphatic group and a saturated aliphatic chain, are common with the description about a repeating unit (block A) and block B, and description is abbreviate | omitted.

The urethane (meth) An example of acrylate and to have a saturated cyclic aliphatic group R to have a ^first structure A to, saturated with fat shackles R ² (includes random) structure B and a saturated cyclic aliphatic group R ³ Structure C It can illustrate a structure comprising a. The structure b is an optional component.

-CO-NH-R ^1- NH-CO-... (Structure A)

^-O-R 2 -CO- ... (Structure B)

-O-R ^3- O-... (Structure C)

The said urethane (meth) acrylate is (meth) acrylate or (meth), for example in addition to the diisocyanate containing R <^1> , the ester containing R <^2> (it is used arbitrarily), and the diol containing R <^3> . ) Can be obtained using an isocyanate having an acryl group and can be easily produced.

As an example, the ratio of the structure A, the structure B, and the structure C is m + 1: m (r + s): m, m + 1: k + n: m, m: m (r + s): m + 1 Or m: k + n: m + 1. M represents an integer of 1 to 4, r and s represent an integer of 0 to 2, respectively, while the sum of r and s is 1 to 2, k represents an integer of 0 to 2, and n is 0 It represents the integer of -2.

Although the method of synthesize | combining a urethane (meth) acrylate is not specifically limited, As an example, the method of first synthesizing a bifunctional intermediate, and synthesizing the isocyanate which has a (meth) acrylate or a (meth) acryl group to the both ends of an intermediate body is mentioned. Can be mentioned.

Specifically, a method of synthesizing the urethane (meth) acrylate corresponding to the repeating unit of the general formula (1) described above, [1] an ester having R ² and a diol having R ³ , m (r The reaction is carried out at a molar ratio of + s): m, and the diisocyanate having m + 1 mol of R ¹ is reacted to obtain an intermediate having -N = C═O groups at both terminals. [2] Then, urethane (meth) acrylate represented by following General formula (8) can be obtained by making 2 mol of (meth) acrylates react with 1 mol of said intermediates.

[Formula 24]

(In general formula (8), R <^1> represents a saturated cyclic aliphatic group, R <^2> represents the saturated aliphatic chain containing a C5-10 linear or branched chain structure, and R <^3> is a saturated cyclic aliphatic group different from R <^1>. R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom, a methyl group or an ethyl group, m represents an integer of 1 to 4, r and s each represent an integer of 0 to 2, and r The sum of and s is 1 to 2, x represents an integer of 0 to 3)

Examples of the method for synthesizing the urethane (meth) acrylates corresponding to the repeating unit of formula (2), a diol with a diisocyanate and R ³ having the ^{[1] R 1 m + 1} : the reaction in a molar ratio of m To obtain an intermediate having an -N = C = O group at both ends. [2-1] Then, 2 moles of (meth) acrylate is reacted with 1 mole of the intermediate, or [2-2] k + n mole of R ² is reacted with 1 mole of the intermediate. After reacting an ester having 2 moles of (meth) acrylate, or [2-3] to 2 moles of (meth) acrylate, an ester having k + n mole R ² is obtained. The urethane (meth) acrylate corresponding to the repeating unit represented by General formula (9) can be obtained by either of the methods of making (meth) acrylate react with the said 1 mol of said intermediates.

[Formula 25]

(In general formula (9), R <^1> represents a saturated cyclic aliphatic group, R <^2> represents the saturated aliphatic chain containing a C5-10 linear or branched chain structure, and R <^3> is a saturated cyclic aliphatic group different from R <^1>. R <^4> represents a hydrogen atom or a methyl group, R <^5> represents a hydrogen atom, a methyl group, or an ethyl group, m represents the integer of 1-4, k represents the integer of 0-2, n represents 0-2 An integer, x represents an integer of 0 to 3)

Examples of the method for synthesizing the urethane (meth) acrylates corresponding to the repeating unit of formula (3), the ester having a diisocyanate and R ² having a ^{[1] R 1, m:} m (r + s) Reaction is carried out at a molar ratio of, and a diol having m + 1 mol of R ³ is reacted to obtain an intermediate having hydroxyl groups at both terminals. [2] Then, urethane (meth) acrylate corresponding to the repeating unit represented by General formula (10) can be obtained by reacting the isocyanate which has 2 mol of (meth) acryl groups with respect to 1 mol of intermediates.

[Formula 26]

(In General Formula (10), R ¹ represents a saturated cyclic aliphatic group, R ² represents a saturated aliphatic chain including a straight or branched chain structure having 5 to 10 carbon atoms, and R ³ represents a saturated cyclic aliphatic group different from R ^1. R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom, a methyl group or an ethyl group, m represents an integer of 1 to 4, r and s each represent an integer of 0 to 2, and r The sum of and s is 1 to 2, x represents an integer of 0 to 3)

Examples of the method for synthesizing the urethane (meth) acrylates corresponding to the repeating unit of formula (4), a diol with a diisocyanate and R ³ having the ^[1] R 1 m: the reaction in a molar ratio of m + 1 To obtain an intermediate having hydroxyl groups at both ends. [2-1] Thereafter, an isocyanate having 2 moles of (meth) acrylate is reacted with 1 mole of the intermediate, or [2-2] 1 mole of the intermediate, with k + n moles of After reacting an ester having R ² , an isocyanate having 2 moles of (meth) acrylate is reacted or k + n mol of R relative to an isocyanate having [2-3] 2 moles of (meth) acryl group. Urethane (meth) corresponding to the repeating unit represented by General formula (11) according to any of the methods of making the urethane (meth) acrylacrylate obtained by making ester which has ² react with respect to 1 mol of said intermediates. An acrylate can be obtained.

[Formula 27]

(In General Formula (11), R ¹ represents a saturated cyclic aliphatic group, R ² represents a saturated aliphatic chain including a linear or branched chain structure having 5 to 10 carbon atoms, and R ³ represents a saturated cyclic aliphatic group different from R ^1. R <^4> represents a hydrogen atom or a methyl group, R <^5> represents a hydrogen atom, a methyl group, or an ethyl group, m represents the integer of 1-4, k represents the integer of 0-2, n represents 0-2 An integer, x represents an integer of 0 to 3)

The structure of the typical monomer which produces block B is shown below.

[Formula 28]

(In General Formula (12), R ⁶ represents a saturated cyclic aliphatic group, R ⁷ represents a hydrogen atom or a methyl group, and y and z are integers of 0 to 2).

The thiol (R-SH) used in the present invention has the thioether structure (RS-) and the hydrocarbon R as described above, except that the H-phase H is a single bond during the reaction with the urethane (meth) acrylate. Since it is common in the point and the specific example of hydrocarbon R was already demonstrated by the thioether structure mentioned above, description about hydrocarbon R is not repeated.

Representative thiols that produce thioether structures are shown below.

[Formula 29]

(In General Formula (13), R ⁸ represents an alkyl chain having 1 or 2 carbon atoms in which a hydrogen atom may be substituted with a methyl group, and n represents an integer of 1 to 4).

Moreover, the other structure of the typical thiol which produces | generates a thioether structure is shown below.

[Formula 30]

(In General Formula (14), R ⁹ represents an alkyl chain having 1 or 2 carbon atoms in which a hydrogen atom may be substituted with an alkyl group, R ¹⁰ represents a hydrogen atom or a methyl group, and q represents an integer of 1 to 4).

In the general formula (14), R ⁹ is an ethyl chain, and the methyl group is bonded to the β carbon of the ethyl chain, q represents the preferred thiol is 4 or below. This thiol is tetrafunctional and forms a thioether structure that forms a complex three-dimensional structure with repeating units.

[Formula 31]

Preparation of an energy-beam curable composition adds and implements the photoinitiator which starts superposition | polymerization of a monomer to the monomer which produces a repeating unit. In another aspect, preparation of an energy-beam curable composition is performed by adding a photoinitiator to the monomer and / or thiol which produce block B in addition to the monomer which produces | generates a repeating unit (block A).

Examples of the photopolymerization initiator include cation such as acetphenone series, benzophenone series, thioxanthone series, benzoin, and radical polymerization initiators such as benzoin methyl ether, aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, and metallocene compounds. A polymerization initiator can be used individually or in combination suitably.

You may add various additives, such as a ultraviolet absorber, a leveling agent, and an antistatic agent, which were mentioned above by << protective film >> to an energy-beam curable composition.

In the energy ray-curable composition, each ratio of the monomer (the total amount of the monomer generating the repeating unit (block A) and the monomer generating the block B), the thiol, the photopolymerization initiator and any of various additives is determined by the type of each material. Therefore, although it is difficult to define uniquely, the sum total of a monomer and a thiol is 50 weight% or more, 99 weight% or less, 0.5 weight% or more, 10 weight% or less, and various additives 0.01 weight% or more as an example. And 50 weight% or less. Moreover, you may add organic solvents, such as toluene, to an energy-beam curable composition.

The weight ratio of monomer A which produces block A and monomer B which produces block B should make the degree of the tensile elasticity improvement of the protective film resulting from block B desirable, and monomer A: monomer B = 70: 30-15: It is preferable that it is the range of 85, It is more preferable that it is 60: 40-15: 85, It is especially preferable that it is 50: 40-15: 85.

With respect to the thiol, the weight ratio of the monomer (monomer A or a mixture of monomer A and monomer B) and the thiol to form the thioether structure should make the degree of tensile strength improvement of the protective film due to the thioether structure desirable. , Monomer: thiol = 95: 5 to 50:50 is preferred, and more preferably 90:10 to 70:30.

In order to apply the prepared energy-beam curable composition on the film base material or the release layer of the film base material, in consideration of continuous productivity, it is preferable to use a coating method such as a roll coating method or a gravure coating method. By the said coating method, an energy-beam curable composition can be apply | coated so that a thin layer, for example, 50 micrometers or less, preferably 30 micrometers or less of a protective film is formed.

Curing in a process (A2) can be performed by irradiating an ultraviolet-ray from an ultraviolet irradiation device. Although the ultraviolet light source to be used is not particularly limited, for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excited mercury lamp, a metal halide lamp, etc. Can be used. When using the adhesive agent which uses an epoxy compound as an active energy ray curable component, considering the absorption wavelength which a general polymerization initiator shows, the high pressure mercury lamp or metal halide lamp which has much light of 400 nm or less is used suitably as an ultraviolet light source.

By hardening an energy-beam curable composition, a protective film is formed on the film base material or on the release layer of a film base material, and the film laminated body which laminated | stacked the protective film on the film base material can be obtained. Moreover, a single protective film can also be obtained by peeling a protective film from a film laminated body.

[Functional layer formation process]

As a modification of the manufacturing method of a film laminated body, the manufacturing method containing a functional layer formation process (B) is mentioned before protective film formation process (A1) and (A2). A functional layer formation process (B) apply | coats an energy-beam curable composition which is a raw material of a functional layer, and hardens on a film base material or the mold release layer of a film base material, and forms a functional layer on a film base material.

Although it does not specifically limit as said functional layer, The hard coat layer, anti-glare layer, and antireflection layer mentioned above are mentioned. The energy ray curable composition which is a raw material of a functional layer contains resin etc. which were mentioned above in description of a hard-coat layer, an anti-glare layer, and an antireflection layer. Moreover, organic solvents, such as methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone (MIBK), isopropyl alcohol (IPA), and toluene, may be added.

In order to apply the energy-beam curable composition which is a raw material of a functional layer on a film base material or the release layer of a film base material, in consideration of continuous productivity, it is preferable to use coating methods, such as a roll coating method and a gravure coating method. . According to the energy-beam curable composition to be used, after heating arbitrarily, you may use the method of bridge | crosslinking and hardening by ultraviolet irradiation etc.

When a functional layer is formed in a film base material in a functional layer formation process, in a protective film formation process (A1), the energy-beam curable composition containing a urethane (meth) acrylate is apply | coated to the functional layer side of a film base material. When a functional layer is multiple layers, it apply | coats to the functional layer side formed last.

When using the film base material with an unevenness | corrugation, unevenness | corrugation is formed in the functional layer formed in the said film base material, and functions as an anti-glare layer which has anti-glare property. The shape of the concavities and convexities is determined according to the required anti-glare properties, and a more preferable concave-convex shape can be defined according to the roughness coefficient Ra, Ra: 0.01 µm or more, Sm: 50 µm to 500 µm, average inclination angle: 0.1 It is more preferable that it is ° -3.0 degrees.

When forming a functional layer, you may form multiple layers. For example, when forming a some hard-coat layer, a 1st hard-coat layer is formed on a film base material or on the release layer of a film base material, and a 2nd hard-coat layer is formed on a 1st hard-coat layer. do. Then, in a process (A1), the energy-beam curable composition containing a urethane (meth) acrylate is apply | coated to the 2nd hard-coat layer side. An anti-glare layer may be formed instead of the second hard coat layer.

In addition, when forming an antireflection layer, a low refractive index layer is formed on a film base material or on a release layer of a film base material, and a high refractive index layer is formed on the said low refractive index layer. In the step (A1), an energy ray curable composition containing urethane (meth) acrylate is applied to the high refractive index layer side. Thereby, the film laminated body laminated | stacked in the order of a film base material, a functional layer, and a protective film can be obtained.

<< manufacturing method of polarizing plate >>

The polarizing plate which concerns on this invention is equipped with the protective film which concerns on this invention in at least one surface of a polarizing film. In the manufacturing method of the polarizing plate which concerns on this invention, it is important to bond the said protective film to a polarizing film, and the bonding method should just employ | adopt a well-known method, and is not specifically limited.

Although a protective film may be used independently as a protective film, it is preferable to use a protective film with a film laminated body, ie, a film base material from the point which is easy to handle.

For example, after a protective film formation process or a functional layer formation process and a protective film formation process, after obtaining the laminated body provided with a protective film, if it bonds to a polarizing film toward the protective film side of the said film laminated body, this invention It is possible to obtain a polarizing plate according to.

The process related to the manufacturing method of a polarizing plate is demonstrated more concretely. The following steps (C1) to (C4) are carried out after the protective film forming step or after the functional layer forming step and the protective film forming step.

(C1) Coating process of apply | coating UV cure adhesive to the protective film side (or polarizing film) of a film laminated body,

(C2) A bonding step of overlapping and pressing the polarizing film (or the protective film side of the film laminate) on the surface of the ultraviolet curable adhesive applied in the coating step,

(C3) Hardening process which hardens an ultraviolet curable adhesive agent by irradiating an ultraviolet-ray from an ultraviolet irradiation device with respect to the film laminated body which the protective film bonded together to the polarizing film through an ultraviolet curable adhesive agent,

(C4) The peeling process of peeling and removing a film base material (support base material) from a laminated film as needed.

In coating process (C1), an ultraviolet curable adhesive agent is apply | coated to the protective film side of a film laminated body used as a bonding surface of a polarizing film (or, instead of the protective film side of a film laminated body, an ultraviolet curable adhesive agent is apply | coated to a polarizing film. do). As a coating machine used here, a well-known thing can be used suitably, For example, the coating machine etc. which use a gravure roll are mentioned.

In pasting process (C2), after going through a coating process (C1), bonding is performed, superimposing and pressing a polarizing film on the adhesive agent application surface of a film laminated body (The ultraviolet curable adhesive was apply | coated to a polarizing film in a coating process (C1). In the case, bonding is performed, pressing the protective film side of a film laminated body on the ultraviolet curable adhesive surface, and pressing. Although well-known means can be used for the pressurization in a bonding process, the method of fitting by a pair of nip rolls is used preferably from a viewpoint that the pressurization during continuous conveyance is possible, and the pressure at the time of pressurization is a pair of It is preferable to set it as about 150-500 N / cm by the linear pressure in the case of being fitted by a nip roll.

In a hardening process (C3), after bonding a film laminated body to a polarizing film, an ultraviolet-ray is irradiated from an ultraviolet irradiation device and hardening an ultraviolet curable adhesive. Ultraviolet rays are irradiated over the film stack. The ultraviolet light source to be used is not particularly limited, but has a light emission distribution at a wavelength of 400 nm or less, for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excited mercury lamp, a metal halide lamp, and the like. Can be used. When using the adhesive agent which uses an epoxy compound as an energy-beam curable component, considering the absorption wavelength which a general polymerization initiator shows, the high pressure mercury lamp or metal halide lamp which has much light of 400 nm or less is used suitably as an ultraviolet light source.

Peeling process (C4) is a process performed suitably as needed, and peels and removes the film base material laminated | stacked on the protective film by this process (when a film base material is multiple layers, a part of film base material is peeled off and Can be removed), thereby obtaining a polarizing plate. In the case where the polarizing plate is further processed, the case where the surface of the protective film is to be protected in the post-processing step or the like may be peeled off after completion of these processing.

EXAMPLE

Hereinafter, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited to the content of an Example. The protective film (protective film and functional layer, when a functional layer is formed in a film base material) which peeled the polyester film base material from the obtained film laminated body is made into the measurement object, and the moisture permeability and tensile strength of the said protective film are the following measurements It was measured by the method.

[Film thickness]

The film thickness of the protective film (or protective film + functional layer) was measured using the digital linear gauge D-10HS and the digital counter C-7HS (made by Ozaki Corporation).

[Water vapor transmission rate]

According to the moisture permeability test method (Cup method) of JISZ0208, the number of grams of water vapor which passes through for 24 hours per 1 m <^{2> of} test pieces in the atmosphere of temperature 40 degreeC and 90% RH of humidity was measured about the protective film.

[Independence]

About the sample film which cut | disconnected the protective film to the size of 15 mm x 160 mm, the long side was made into the tension direction, and it used the "Tenshiron 'RTF-24" (made by Yamato Scientific Co., Ltd.) so that the holding section may be 100 mm. The both ends were held by a holding tool, and the tensile modulus and / or tensile strength were determined from the maximum slope of the stress-strain curve in the measurement load range of 40 N and the measurement speed of 20 mm / min at room temperature (25 ° C).

In evaluation of independence, when the tensile elasticity modulus of the sample film is 1500 Mpa or more and less than 2500 Mpa, it determined with (circle), and when tensile elasticity modulus is 2500 Mpa or more, it determined with (circle), and in the case of (circle) or (double), it determined with self-reliance. On the other hand, when the film | membrane formed in the step peeled from PET film fell, it was determined as x as unmeasurable.

On the other hand, in the case of tensile strength, when the tensile strength of the sample film is 15 MPa or more and less than 25 MPa, it is determined as ○, when the tensile strength is 25 MPa or more, it is determined as ◎, and in the case of ○ or ◎, it is determined as having self-reliance. It was. On the other hand, when the film | membrane formed in the step peeled from PET film fell, it was determined as x as unmeasurable.

[Production Example 1]

Synthesis of Compound 1:

196.29 g (1 mol) of tricyclodecane dimethanol and 228.29 g (2 mol) of epsilon -caprolactone were put into a flask, and it heated up to 120 degreeC, and added 50 ppm of monobutyltin oxides as a catalyst. Thereafter, the reaction was carried out under nitrogen gas flow until the remaining ε-caprolactone became 1% or less by gas chromatography to obtain diol (1).

444.58 g (2 mol) of isophorone diisocyanate was added to another flask, and dihydroxy (1) 425.57 g (1 mol) was added at a reaction temperature of 70 deg. C to 2-hydroxyethyl acrylate when the remaining isocyanate group became 5.7%. 232.24 g (2 moles) and 0.35 g of dibutyltin laurate are added and the reaction is carried out until the remaining isocyanate group becomes 0.1%, thereby producing a urethane acrylate (Compound 1) which is a monomer that generates a repeating unit (block A). Obtained (m is 1 in the general formula (1a) of the repeating unit of compound 1).

[Production Example 2]

Synthesis of Compound 2:

114.14 g (1 mol) of epsilon -caprolactone and 116.12 g (1 mol) of 2-hydroxyethyl acrylate were reacted at 120 degreeC under nitrogen stream, and it was made to 100 weight part of 114.14 g (1 mol) of epsilon -caprolactone. 5 parts by weight of spherical activated carbon BAC, Inc. was added as a catalyst, and 500 mg / Kg of 4-methoxyphenol was added to the entire polymerization system in order to suppress radical polymerization of 2-hydroxyethyl acrylate. Then, reaction was performed until (epsilon) -caprolactone became 1% or less by gas chromatography, and (epsilon) -caprolactone modified hydroxyethyl acrylate (2) was obtained.

444.58 g (2 mol) of isophorone diisocyanate was added to the flask, and 196.29 g (1 mol) of tricyclodecane dimethanol was added at a reaction temperature of 70 ° C, and the ε-caprolactone modified hydroxide was added when the remaining isocyanate group became 5.7% 460.52 g of 2 moles of oxyethyl acrylate (2) was added, and the reaction was carried out until the remaining isocyanate group became 0.1% to obtain a urethane acrylate (compound 2), which is a monomer that produces a repeating unit (the repeating unit of compound 2 is And m is 1 in general formula (2a).

[Manufacture example 3]

The compound 1a which is a monomer which produces a repeating unit was obtained like manufacture example 1 except having changed the synthesis | combination amount of diol (1) twice and changing the usage-amount of isophorone diisocyanate from 2 mol to 3 mol (compound 1a). In the repeating unit of 1a, m is 2 in General Formula (1a).

[Production Example 4]

Compound 1b was obtained in the same manner as in Production Example 1 except that the synthesis amount of the diol (1) was changed three times and the amount of isophorone diisocyanate changed from 2 mol to 4 mol (the repeating unit of compound 1b was general M is 3 in Formula (1a).

Example 1 Polyester Film Substrate / Protective Film

Using the applicator, the following energy-beam curable composition (1) for protective film formation was apply | coated to the peeling layer side of Panax non-silicone peeling PET SG-1 (38 micrometer thickness). Energy-beam curable composition (P1) contains toluene, and solid content fraction (NV) is 60%.

The coating thickness of the energy ray-curable composition (P1) was adjusted so that the film thickness after drying was 20 µm to 30 µm. In the set to dry in the temperature 100 ℃ clean oven, the coating dry film and, then, by ultraviolet rays with a peak intensity 326mW / cm ^2, accumulated light quantity condition of 192mJ / cm ² cured in a nitrogen atmosphere, one side of a PET film The film laminated body in which the protective film was formed was obtained. Table 7 shows the evaluation results for this film laminate.

[Example 2: Polyester film base material / HC layer / protective film]

By the reverse coating method, the following energy-beam curable composition for HC layer formation (HC1) was apply | coated to the peeling layer side of Panax non-silicone peeling PET SG-1 (38 micrometer thickness). The formed coating film was dried at 100 ° C. for 1 minute, and was irradiated with ultraviolet light using a 120 W / cm condensing type high pressure mercury lamp of one lamp in a nitrogen atmosphere (irradiation distance 10 cm, irradiation time 30 seconds) to cure the coating film. Then, a hard coat layer (HC layer) having a thickness of 2.5 μm and a refractive index of 1.52 was formed.

Subsequently, the energy-beam curable composition (P1) of Example 1 was apply | coated and dried in the same conditions as Example 1 on the said HC layer side, and the film laminated body in which the protective film was formed in the HC layer side was obtained. Table 7 shows the evaluation results for this film laminate.

[Example 3: Polyester film base material / AG layer (filler containing) / protective film]

The coating solution for a release layer is coated by the bar coating method so that a dry film thickness may be set to 2 micrometers on one side of PET film (Product name: Emblem S-50 made from Unitica) which becomes a support body of a release film, and coating The membrane was dried at 140 ° C. for 1 minute and then cured. In this manner, a support having a release layer having a thickness of 2 μm having surface irregularities on the PET film was obtained. Next, the following energy-beam curable composition for AG layer formation (AG1) was apply | coated on the said release layer.

The coating thickness was adjusted so that a dry film thickness might be 6 micrometers by the bar coating system. After drying the coating film of AG1 for 1 minute at 100 degreeC, it irradiated with ultraviolet-ray (lamp: high pressure mercury lamp, lamp output: 120W / cm, accumulated light quantity: 120mJ / cm), and hardened the coating film. Subsequently, the energy-beam curable composition (P1) of Example 1 was apply | coated and dried on the AG layer side on the same conditions as Example 1, and the film laminated body in which the protective film was formed on the AG layer side was obtained. Table 7 shows the evaluation results for this film laminate.

[Example 4: Polyester film base material / HC layer (fillerless AG) / protective film]

The coating liquid for a release layer is coated by the bar coating method so that a dry film thickness may become 2 micrometers on one side of PET film (Product name: Emblem S-50 made from Unitica) which becomes a support body of a release film, and a coating film is After drying for 1 minute at 140 ℃, it was cured. In this manner, a support having a release layer having a thickness of 2 μm having surface irregularities on the PET film was obtained. Subsequently, it carried out similarly to the application | coating of AG1 of Example 3, and hardened | cured after apply | coating the following energy-beam curable composition (HC2) for HC layer formation on the said release layer.

Subsequently, the energy-beam curable composition (P1) of Example 1 was apply | coated and dried on the said HC layer side on the conditions similar to Example 1, and the film laminated body with a protective film formed on the HC layer side was obtained. Table 7 shows the evaluation results for this film laminate.

[Example 5: Polyester film base material / low refractive index layer / high refractive index layer and AG layer / protective film]

The coating liquid for a release layer is coated by the bar coating method so that a dry film thickness may be set to 2 micrometers on one side of PET film (Product name: Emblem S-50 made from Unitica) which becomes a support body of a release film, and coating The membrane was dried at 140 ° C. for 1 minute and then cured. In this manner, a support having a release layer having a thickness of 2 μm having surface irregularities on the PET film was obtained.

By the reverse coating method, the following low-refractive-index paint (LR1) was apply | coated on the said release layer, and the coating film was dried at 100 degreeC for 1 minute, and the low-refractive-index layer with the unevenness | corrugation of 0.1 micrometer thickness and 1.38 refractive index was formed. . Then, it left still at 60 degreeC for 120 hours for hardening of the low refractive index layer.

Subsequently, by the bar coating method, the energy-beam curable composition for AG layer formation (AG1) described in Example 3 was apply | coated on the said low refractive index layer so that dry film thickness might be 6 micrometers, and it dried at 100 degreeC for 1 minute, It was irradiated with ultraviolet rays (lamp: high pressure mercury lamp, lamp output: 120 W / cm, accumulated light amount: 120 mJ / cm ² ), and the coating film was cured to form an AG layer.

Subsequently, the energy-beam curable composition (P1) of Example 1 was apply | coated and dried on the said AG layer side on the same conditions as Example 1, and the film laminated body with a protective film formed on the AG layer side was obtained. Table 7 shows the evaluation results for this film laminate.

[Example 6: Polyester film base material / low refractive index layer / high refractive index layer and HC layer / protective film]

Using an applicator, the low refractive index coating material (LR1) described in Example 5 was coated on the release layer side of Panax non-silicone release PET SG-1 (38 μm thick), and the coating film was dried at 100 ° C. for 1 minute. It hardened | cured and formed the low refractive index layer of thickness 0.1micrometer and refractive index 1.38. Then, it left still at 60 degreeC for 120 hours for hardening of the low refractive index layer.

Next, the following energy-beam curable composition for HC layer formation (HC3) was apply | coated on the said low refractive index layer by the reverse coating method. After drying at 100 ° C. for 1 minute, ultraviolet irradiation (irradiation distance 10 cm, irradiation time 30 seconds) was performed with one lamp of 120 W / cm condensing type high pressure mercury lamp in a nitrogen atmosphere, and the coating film was cured to give a thickness of 2.5 μm and a refractive index of 1.64 HC. A layer was formed.

Subsequently, the energy-beam curable composition (P1) of Example 1 was apply | coated and dried on the said HC layer side on the same conditions as Example 1, and the film laminated body in which the protective film was formed on the HC layer side was obtained. Table 7 shows the evaluation results for this film laminate.

[Examples 7-9: Polyester film base material / protective film]

In Example 7, Compound 1 was changed to Compound 2, in Example 8, Compound 1 was changed to Compound 1a, and in Example 9, Compound 1 was changed to Compound 1b, except for the above-described changes, in the same manner as in Example 1 The film laminated body in which the protective film was formed in one side of PET film was obtained. Table 7 shows the evaluation results for this film laminate.

Comparative Example 1

A cured film was formed on one side of a PET film in the same manner as in Example 1, except that Compound 1 was changed to Compound 3 (manufactured by Shin-Nakamura Chemical Co., Ltd.) represented by the following General Formula (12a) to form a film laminate. Got it. Table 7 shows the evaluation results for this film laminate.

[Formula 32]

As shown in Table 7, when the compound 1 of Examples 1-6 and the compound 2 of Example 7 were used, the protection film of very low moisture permeability was obtained. In Examples 2 to 6, the water vapor transmission rate is lowered by the functional layer. A high value can also be obtained for the tensile modulus and a very useful protective film can be obtained. The protective films which use compounds 1a and 1b in Examples 8 and 9 are inferior to those of Example 1 (compound 1), but achieve low moisture permeability. Moreover, evaluation of tensile elasticity modulus is (circle) and sufficient self-reliance is obtained as a protective film which concerns on this invention.

On the other hand, the cured film formed in the comparative example 1 is very hard and fragile, and when it peels from a PET film, it collapses, and the film thickness, moisture permeability, and tensile strength could not be measured, and there was no independence. When synthesize | combining the compound 3, since the monomer which has only one type of saturated cyclic aliphatic group was used, the repeating unit of compound 3 contains only one type of saturated cyclic aliphatic group. For this reason, the cohesion force between repeating units becomes high too much and it can be considered that the cured film with high brittleness was formed.

Example 10 Polyester Film Substrate / Protective Film

Using the applicator, the following energy-beam curable composition (P2) for protective film formation was apply | coated to the peeling layer side of Panax non-silicone peeling PET SG-1 (38 micrometer thickness). Energy-beam curable composition (P2) contains toluene, and solid content fraction (NV) is 60%.

The coating thickness of the energy beam curable composition (P2) adjusted the coating conditions so that the film thickness after drying might be 20 micrometers-30 micrometers. In a clean oven set to the temperature 100 ℃ by drying, followed by drying the coating film, and thereafter, by an ultraviolet with a peak illumination condition 326mW / cm ^2, accumulated light amount of 192mJ / cm ² cured in a nitrogen atmosphere, one of the PET film The film laminated body in which the protective film was formed in the surface was obtained. Table 9 shows the evaluation results for this film laminate.

Example 11: Polyester Film Substrate / Protective Film

A film having a protective film formed on one side of a PET film in the same manner as in Example 10 except that the monomer (95 parts by weight of compound 1) used in Example 10 was changed to 66.5 parts by weight of compound 1 and 28.5 parts by weight of compound 3 A laminate was obtained. Compound 3 is a monomer which produces block B, and is represented by following General formula (12a). Table 9 shows the evaluation results for the film laminate.

[Formula 33]

[Example 12: Polyester film base material / protective film]

A film having a protective film formed on one side of a PET film in the same manner as in Example 10 except that the monomer (95 parts by weight of compound 1) used in Example 10 was changed to 47.5 parts by weight of compound 1 and 47.5 parts by weight of compound 3 A laminate was obtained. Table 9 shows the evaluation results for this film laminate.

[Example 13: Polyester film base material / HC layer / protective film]

In the same manner as in Example 2, the HC layer was formed on the PET film (PET SG-1). Subsequently, the energy-beam curable composition used in Example 12 was apply | coated and dried on the said HC layer side on the same conditions as Example 12, and the film laminated body with a protective film formed on the HC layer side was obtained. Table 9 shows the evaluation results for this film laminate.

[Example 14: Polyester film base material / AG layer (filler containing) / protective film]

In the same manner as in Example 3, the coating film of AG1 was cured on a PET film (Product name: Emblem S-50 manufactured by Unitica). Subsequently, the energy-beam curable composition used in Example 12 was apply | coated and dried on the AG layer side on the same conditions as Example 12, and the film laminated body with a protective film formed on the AG layer side was obtained. Table 9 shows the evaluation results for this film laminate.

[Example 15: Polyester film base material / HC layer (fillerless AG) / protective film]

In the same manner as in Example 4, an HC layer was formed on a PET film (product name: Unit S-50 made by Unitica). Subsequently, the energy-beam curable composition used in Example 12 was apply | coated and dried on the said HC layer side on the same conditions as Example 12, and the film laminated body with a protective film formed on the HC layer side was obtained. Table 9 shows the evaluation results for this film laminate.

[Example 16: Polyester film base material / low refractive index layer / high refractive index layer and AG layer / protective film]

In the same manner as in Example 5, a low refractive index layer was formed on the PET film, and an AG layer was formed on the low refractive index layer. Subsequently, the energy-beam curable composition used in Example 12 was apply | coated and dried on the AG layer side on the same conditions as Example 12, and the film laminated body with a protective film formed on the AG layer side was obtained. Table 9 shows the evaluation results for this film laminate.

[Example 17: Polyester film base material / low refractive index layer / high refractive index layer and HC layer / protective film]

In the same manner as in Example 6, a low refractive index layer was formed on the PET film, and an HC layer was formed on this low refractive index layer. Subsequently, the energy-beam curable composition used in Example 12 was apply | coated and dried on the said HC layer side on the same conditions as Example 12, and the film laminated body with a protective film formed on the HC layer side was obtained. Table 9 shows the evaluation results for this film laminate.

Example 18 Polyester Film Substrate / Protective Film

A film having a protective film formed on one side of a PET film in the same manner as in Example 10 except that the monomer (95 parts by weight of compound 1) used in Example 10 was changed to 28.5 parts by weight of compound 1 and 66.5 parts by weight of compound 3 A laminate was obtained. Table 9 shows the evaluation results for this film laminate.

[Example 19: Polyester film base material / protective film]

A film having a protective film formed on one side of a PET film in the same manner as in Example 10 except that the monomer (95 parts by weight of compound 1) used in Example 10 was changed to 19 parts by weight of compound 1 and 76 parts by weight of compound 3 A laminate was obtained. Table 9 shows the evaluation results for this film laminate.

Comparative Example 2

Except having changed the monomer (95 weight part compound 1) used in Example 10 into 95 weight part compound 3, it carried out similarly to Example 10, and obtained the film laminated body in which the protective film was formed on one side of PET film (compound 1 is not used). Table 9 shows the evaluation results for this film laminate.

Example 20

Except having changed the compound 1 into the compound 2, it carried out similarly to Example 10, the cured film was formed in one side of PET film, and the film laminated body was obtained. Table 9 shows the evaluation results for this film laminate.

Example 21

A cured film was formed on one side of the PET film in the same manner as in Example 20 except that the monomer (95 parts by weight of compound 2) used in Example 20 was changed to 57 parts by weight of compound 2 and 38 parts by weight of compound 3 And the film laminated body were obtained. Table 9 shows the evaluation results for this film laminate.

Example 22

A cured film was formed on one side of a PET film in the same manner as in Example 10 except that the monomer (95 parts by weight of compound 1) used in Example 10 was changed to 95 parts by weight of compound 1a to obtain a film laminate. Table 9 shows the evaluation results for this film laminate.

Example 23

A cured film was formed on one side of a PET film in the same manner as in Example 10 except that the monomer (95 parts by weight of compound 1a) used in Example 22 was changed to 38 parts by weight of compound 1a and 57 parts by weight of compound 3, The film laminated body was obtained. Table 9 shows the evaluation results for this film laminate.

As shown in Table 9, in Example 10, only Compound 1 was used as the monomer and Compound 3 was not used. As a result, the obtained protective film had a water vapor permeability of 77 g / (m ² · 24h in a state of 24 μm in film thickness. Was. Subsequently, in Example 11, as a result of using the compound 3 as the monomer B, the moisture permeability of the obtained protective film was 60 g / (m ² · 24h), and it was found that a low film moisture permeability was obtained.

Next, in Example 12, as a result of increasing the ratio of compound 3, it was confirmed that the moisture permeability was lowered more. In Examples 13-17, as a result of providing a functional layer in a protective film, it turns out that low moisture permeability is maintained. In Example 18 and Example 19, as a result of increasing the ratio of compound 3, it was confirmed that the moisture permeability was further lowered. In addition, the protective films obtained in Examples 11 to 19 have a high tensile modulus, and it is also demonstrated that they have sufficient self-supporting properties.

On the other hand, in Comparative Example 2, as a result of using only Compound 3 as a monomer and not using Compound 1, the resulting cured film was very hard and fragile and collapsed when peeled from a PET film. Thus, measurement of film thickness, moisture permeability and tensile strength was performed. It could not be implemented and there was no independence at all. When synthesize | combining compound 3, the monomer which has only one type of saturated cyclic aliphatic group is used, and compound 3 contains only one type of saturated cyclic aliphatic group. For this reason, it can be considered that the cohesion force between monomer units becomes excessively high and the brittle cured film was formed.

In Example 20, Compound 2 was used as the monomer, and Compound 3 was used in Example 21 in addition to Compound 2. In Example 11, the effect of lowering the moisture permeability was confirmed from the comparison of both examples. From the comparison of Example 22 and Example 23 using the compound 3 as the monomer, in Example 23, the effect of lowering the moisture permeability was confirmed.

Example 24 Polyester Film Substrate / Protective Film

Using the applicator, the energy-beam curable composition (P2) for protective film formation used in Example 10 was apply | coated to the peeling layer side of Panax non-silicone peeling PET SG-1 (38 micrometer thickness). Energy-beam curable composition (P2) contains toluene, and solid content fraction (NV) is 60%.

The coating thickness of the energy beam curable composition (P2) adjusted the coating conditions so that the film thickness after drying might be 20 micrometers-30 micrometers. In the clean oven set to 100 degreeC of drying furnace, the coating film is dried, and it is ultraviolet-hardened on the conditions of peak roughness 326mW / cm <^2> and accumulated light quantity 192mJ / cm <^2> under nitrogen atmosphere, and one side of PET film The film laminated body in which the protective film was formed was obtained. Table 10 shows the evaluation results for this film laminate.

Example 25 Polyester Film Substrate / Protective Film

A film having a protective film formed on one side of a PET film in the same manner as in Example 24 except that the monomer (95 parts by weight of compound 1) used in Example 24 was changed to 90.25 parts by weight of compound 1 and 4.75 parts by weight of compound 4 A laminate was obtained. Compound 4 (manufactured by Showa Denku Co., Ltd.) is a thiol, and the structure thereof is represented by the following General Formula (14a). Table 10 shows the evaluation results for the film laminate.

[Formula 34]

Example 26 Polyester Film Substrate / Protective Film

A film having a protective film formed on one side of a PET film in the same manner as in Example 24 except that the monomer (95 parts by weight of compound 1) used in Example 24 was changed to 85.5 parts by weight of compound 1 and 9.5 parts by weight of compound 4 A laminate was obtained. Table 10 shows the evaluation results for this film laminate.

Example 27 Polyester Film Substrate / Protective Film

A film having a protective film formed on one side of a PET film in the same manner as in Example 24 except that the monomer (95 parts by weight of compound 1) used in Example 24 was changed to 76 parts by weight of compound 1 and 19 parts by weight of compound 4 A laminate was obtained. Table 10 shows the evaluation results for this film laminate.

Example 28 Polyester Film Substrate / Protective Film

A film having a protective film formed on one side of a PET film in the same manner as in Example 24 except that the monomer (95 parts by weight of compound 1) used in Example 24 was changed to 66.5 parts by weight of compound 1 and 28.5 parts by weight of compound 4 A laminate was obtained. Table 10 shows the evaluation results for this film laminate.

Example 29 Polyester Film Substrate / Protective Film

A film having a protective film formed on one side of a PET film in the same manner as in Example 24 except that the monomer (95 parts by weight of compound 1) used in Example 24 was changed to 57 parts by weight of compound 1 and 38 parts by weight of compound 4 A laminate was obtained. Table 10 shows the evaluation results for this film laminate.

[Example 30: Polyester film base material / HC layer / protective film]

In the same manner as in Example 2, the HC layer was formed on the PET film (PET SG-1). Subsequently, the energy-beam curable composition used in Example 26 was apply | coated and dried on the said HC layer side on the same conditions as Example 26, and the film laminated body with a protective film formed on the HC layer side was obtained. Table 10 shows the evaluation results for this film laminate.

[Example 31: Polyester film base material / AG layer (filler included) / protective film]

In the same manner as in Example 3, the coating film of AG1 was cured on a PET film (Product name: Emblem S-50 manufactured by Unitica). Subsequently, the energy-beam curable composition used in Example 26 was apply | coated and dried on the AG layer side on the same conditions as Example 26, and the film laminated body with a protective film formed on the AG layer side was obtained. Table 10 shows the evaluation results for this film laminate.

[Example 32: Polyester film base material / HC layer (fillerless AG) / protective film]

In the same manner as in Example 4, an HC layer was formed on a PET film (product name: Unit S-50 made by Unitica). Subsequently, the energy-beam curable composition used in Example 26 was apply | coated and dried on the said HC layer side on the same conditions as Example 26, and the film laminated body with a protective film formed on the HC layer side was obtained. Table 10 shows the evaluation results for this film laminate.

[Example 33: Polyester film base material / low refractive index layer / high refractive index layer and AG layer / protective film]

In the same manner as in Example 5, a low refractive index layer was formed on the PET film, and an AG layer was formed on the low refractive index layer. Subsequently, the energy-beam curable composition used in Example 26 was apply | coated and dried on the AG layer side on the same conditions as Example 26, and the film laminated body with a protective film formed on the AG layer side was obtained. Table 10 shows the evaluation results for this film laminate.

[Example 34: Polyester film base material / low refractive index layer / high refractive index layer and HC layer / protective film]

In the same manner as in Example 6, a low refractive index layer was formed on the PET film, and an HC layer was formed on this low refractive index layer. Subsequently, the energy-beam curable composition used in Example 26 was apply | coated and dried on the said HC layer side on the same conditions as Example 26, and the film laminated body with a protective film formed on the HC layer side was obtained. Table 10 shows the evaluation results for this film laminate.

Example 35

Except having changed the monomer (95 weight part compound 1) used in Example 24 into 95 weight part compound 2, the film laminated body with a protective film formed on one side of PET film was obtained like Example 24 (compound 1 not used). Table 10 shows the evaluation results for this film laminate.

Example 36 Polyester Film Substrate / Protective Film

A film having a protective film formed on one side of a PET film in the same manner as in Example 24 except that the monomer (95 parts by weight of compound 1) used in Example 24 was changed to 85.5 parts by weight of compound 2 and 9.5 parts by weight of compound 4. A laminate was obtained. Table 10 shows the evaluation results for this film laminate.

Example 37

A film laminate in which a protective film was formed on one side of a PET film was obtained in the same manner as in Example 25 except that the monomer (95 parts by weight of compound 1) used in Example 24 was changed to 95 parts by weight of compound 1a (compound) 1 not used). Table 10 shows the evaluation results for this film laminate.

Example 38 Polyester Film Substrate / Protective Film

A film having a protective film formed on one side of a PET film in the same manner as in Example 24 except that the monomer (95 parts by weight of compound 1) used in Example 24 was changed to 76 parts by weight of compound 1a and 19 parts by weight of compound 4 A laminate was obtained. Table 10 shows the evaluation results for this film laminate.

Example 39

A film laminate in which a protective film was formed on one side of a PET film was obtained in the same manner as in Example 24 except that the monomer (95 parts by weight of compound 1) used in Example 24 was changed to 95 parts by weight of compound 1b (compound) 1 not used). Table 10 shows the evaluation results for this film laminate.

Example 40 Polyester Film Substrate / Protective Film

A film having a protective film formed on one side of a PET film in the same manner as in Example 24 except that the monomer (95 parts by weight of compound 1) used in Example 24 was changed to 90.25 parts by weight of compound 1b and 4.75 parts by weight of compound 4 A laminate was obtained. Table 10 shows the evaluation results for this film laminate.

As shown in Table 10, in Example 24, only Compound 1 was used as the monomer and Compound 4 was not used. As a result, the obtained protective film had a film thickness of 24 µm and a water vapor transmission rate of 77 g / (m ² · 24h), Tensile strength was 20 MPa. Subsequently, in Example 25, the compound 1 which is thiol was used together for the compound 1, The obtained protective film was 25 micrometers in film thickness, the water vapor transmission rate was 86 g / (m <^2> * 24h), and the tensile strength was 30 Mpa. Comparing both results, in Example 25, although the water vapor transmission rate slightly increased, it turns out that the tensile strength is 1.5 times and the drastic increase of tensile strength is achieved.

Next, in Example 26, as a result of increasing the ratio of compound 4, although the moisture permeability was slightly increased than that of Example 25, it was confirmed that the tensile strength was further increased. In Examples 27 and 28, the proportion of compound 4 was increased to 20% and 30%, respectively, but the tensile strength was further increased than that of Example 26. In Example 29, the ratio of compound 4 was further increased to 40%, but the tensile strength was very high, at least three times higher than that of Example 24, but the moisture permeability was very high.

In Examples 30-34, although the functional layer is provided in the protective film, it turns out that the protective film excellent in tensile strength was obtained similarly to Example 26.

In Example 35 and later, Compound 1 was changed to another monomer having plural kinds of saturated cyclic aliphatic groups. In Example 35, when the compound 1 was changed to the compound 2 and the compound 4 which is thiol was not used together, the obtained protective film had a film thickness of 23 micrometers and the water vapor transmission rate was 93 g / (m <^2> * 24h). On the other hand, in Example 36, although thiol compound 4 was used together with 10% of thiol compound 4, the tensile strength became about twice as much as Example 35, and the tendency for the tensile strength of a protective film to become high was confirmed.

In the same manner, Example 37 and Example 38 and Example 40 were carried out for Compound 1a, and Example 39 and Example 40 were carried out for Compound 1a, and the tensile strength of the protective film was increased by using Thiol Compound 4 in combination with Compounds 1a and 1b. The trend could be confirmed.

As is apparent from the evaluation results shown in Table 10, in the production of the protective film, the protective film formed by polymerization by forming a thiol compound together with a urethane (meth) acrylate having a plurality of kinds of saturated cyclic aliphatic groups is formed with low moisture permeability. With this, it is understood to have high independence.

[Industry availability]

Since the protective film which concerns on this invention is low moisture permeability and self-supporting in the state of a thin layer, it is useful as a use member which requires low moisture permeability, especially a constituent member of a polarizing plate, and is applicable to various fields.

Claims

Block A containing the repeating unit which has a structure derived from bifunctional urethane (meth) acrylate which has a some kind of saturated cyclic aliphatic group; And
Block B containing structure derived from bifunctional (meth) acrylate having one kind of saturated cyclic aliphatic group
It is comprised by the copolymer containing the protective film characterized by the above-mentioned.

It contains the polymer chain comprised by the repeating unit which has a structure derived from bifunctional urethane (meth) acrylate which has a several types of saturated cyclic aliphatic group,
At least, the protective film, characterized in that the structure having a thioether bond in the middle of the polymer chain or the terminal of the polymer chain is bonded.

The method according to claim 1,
At least, the protective film, characterized in that a structure having a thioether bond in the middle of the copolymer or the terminal of the copolymer is bonded.

The method according to any one of claims 1 to 3,
The repeating unit,
The following structure A containing a saturated cyclic aliphatic group R ¹ , and
A protective film comprising the following structure C containing a saturated cyclic aliphatic group R ³ .
-CO-NH-R ^1- NH-CO-. (Structure A)
-O-R ^3- O-... (Structure C)

The method according to claim 4,
The repeating unit,
Saturated fat to the shackles including R ² protective film further comprising a structure B.
^-O-R 2 -CO- ... (Structure B)

The method according to claim 5,
Said repeating unit is a structure represented by following General formula (1), The protective film characterized by the above-mentioned.
[Formula 1]

The method according to claim 4,
Said repeating unit is a structure represented by following General formula (2), The protective film characterized by the above-mentioned.
[Formula 2]

The method according to claim 5,
The said repeating unit is a structure represented by following General formula (3), The protective film characterized by the above-mentioned.
[Formula 3]

The method according to claim 4,
Said repeating unit is a structure represented by following General formula (4), The protective film characterized by the above-mentioned.
[Formula 4]

The method according to claim 4,
Said R <^1> is 3-methylene-3,5,5-trimethylcyclohexane ring, R <^3> is a dimethylene tricyclodecane ring, The protective film characterized by the above-mentioned.

The method according to claim 1,
Said block B is a structure represented by following General formula (5), The protective film characterized by the above-mentioned.
[Formula 5]

The method according to claim 11,
R <^6> is tricyclodecane ring, The protective film characterized by the above-mentioned.

The method according to claim 2 or 3,
The structure which has the said thioether bond is a structure represented by following General formula (6), The protective film characterized by the above-mentioned.
[Formula 6]

The method according to claim 2 or 3,
The structure which has the said thioether bond is a structure represented by following General formula (7), The protective film characterized by the above-mentioned.
[Formula 7]

The method according to claim 1 or 2,
While the water vapor transmission rate is 150 g / (m ² · 24 hours) or less,
Moreover, tensile elasticity modulus is 1500 Mpa or more, or tensile strength is 25 Mpa or more, The protective film characterized by the above-mentioned.

On at least one side of the protective film of Claim 1 or 2,
(1) the film base material which supports the said protective film,
(2) a hard coat layer having scratch resistance,
(3) an antiglare layer which scatters light,
(4) The film laminated body provided with any one of the anti-reflection layer comprised from the high refractive index layer provided on the said protective film, and the low refractive index layer provided in the said high refractive index layer.

At least one surface of a polarizing film is equipped with the protective film of Claim 1 or Claim 2, The polarizing plate characterized by the above-mentioned.