KR20110092217A - Liquid crystal display device, method of manufacturing the same, and polymer composition - Google Patents

Abstract

PURPOSE: A liquid crystal display element, manufacturing method thereof, polymer composition are provided to have wide viewing angle and have high reliability. CONSTITUTION: A manufacturing method of a liquid crystal display element includes as follows. A block(3) is formed by spraying polymer composition containing organic solvent. A liquid crystal cell is arranged by facing the block by interposing a pair of substrate formed on the block on a layer of a liquid crystal molecule layer.

Description

Liquid crystal display element, its manufacturing method, and a polymer composition {LIQUID CRYSTAL DISPLAY DEVICE, METHOD OF MANUFACTURING THE SAME, AND POLYMER COMPOSITION}

This invention relates to the manufacturing method of a liquid crystal display element. More specifically, the present invention relates to a novel method for producing a liquid crystal display device having a wide viewing angle and a fast response speed.

Among the liquid crystal display elements, an MVA (Multi-Domain Vertical Alignment) panel conventionally known as a vertical alignment mode forms projections in the liquid crystal panel, thereby restricting the falling direction of the liquid crystal molecules, thereby increasing the viewing angle. However, according to this system, the lack of transmittance and contrast derived from the projections is inevitable, and there is a problem that the response speed of the liquid crystal molecules is slow.

Recently, in order to solve the above problems of the MVA panel, a PSA (Polymer Sustained Alignment) mode has been proposed. PSA mode is a polymerizable compound in a gap between a pair of substrates formed of a substrate with a patterned conductive film and a substrate with a conductive film not having a pattern, or a gap of a pair of substrates formed of two substrates with a patterned conductive film. The liquid crystal composition containing the polymer is sandwiched, and the polymerizable compound is polymerized by irradiating ultraviolet rays in a state where a voltage is applied between the conductive films, thereby expressing a pretilt angle characteristic to control the alignment direction of the liquid crystal. Technology. According to this technique, by setting the conductive film in a specific configuration, it is possible to increase the viewing angle and to speed up the liquid crystal molecular response, and also to solve the problem of lack of transmittance and contrast which is inevitable in the MVA panel. In the PSA mode, however, irradiation of a large amount of ultraviolet light, for example 100,000 J / m 2, is required for the polymerization of the polymerizable compound, which causes a problem that the liquid crystal molecules are decomposed. It is clear that unreacted compounds which have not been left in the liquid crystal layer are caused to interact with each other, resulting in display unevenness, adversely affecting voltage integrity characteristics, or causing problems in long-term reliability of the panel.

Non-patent document 1 has proposed the method of using the liquid crystal aligning film formed from the polyimide-type liquid crystal aligning agent containing reactive mesogen (mesogen). According to the nonpatent literature 1, the liquid crystal display element provided with the liquid crystal aligning film formed by such a method says that the response of a liquid crystal molecule is high speed. However, Non-Patent Literature 1 does not describe any reactive mesogen in what amount, and there is still a large amount of ultraviolet irradiation required, and there is no concern about display characteristics, especially voltage integrity characteristics. .

Japanese Laid-Open Patent Publication No. 2010-97188 Japanese Patent Application Laid-Open No. 5-107544

 Y.-J. Lee et al., SID 09 DIGEST, p. 666 (2009)  T. J. Scheffer et al., J. Appl. Phys. vol. 48, p. 1783 (1977)  F. Nakano, et al., JPN. J. Appl. Phys. vol. 19, p. 2013 (1980)

This invention is made | formed in view of the said situation, and an object of this invention is to provide the manufacturing method of the liquid crystal display element which has a wide viewing angle, the response speed of liquid crystal molecules is fast, and was excellent in display characteristics and long-term reliability.

According to this invention, the said subject of this invention is

On the said conductive film of a pair of board | substrates which have a conductive film, respectively

(A) the following formula (A-I):

(In formula (AI), R is a hydrogen atom or a methyl group, and Y ¹ and Y ² are each independently an oxygen atom or a sulfur atom.)

A polymer having a group represented by

(C) organic solvent

A coating film is formed by applying a polymer composition containing

A pair of substrates on which the coating film is formed are disposed to face each other such that the coating film is opposed to each other via a layer of liquid crystal molecules to form a liquid crystal cell,

It is achieved by a method for manufacturing a liquid crystal display device which undergoes a step of irradiating light to the liquid crystal cell in a state where a voltage is applied between the conductive films of the pair of substrates.

The liquid crystal display device produced by the method of the present invention has a wide viewing angle, a fast reaction rate of liquid crystal molecules, exhibits sufficient transmittance and contrast, excellent display characteristics, and no display characteristics deterioration even when continuously driven for a long time. .

In addition, according to the method of the present invention, since the amount of light required for irradiation is at least minimized, there is no problem of liquid crystal molecule decomposition, which also contributes to the reduction of the manufacturing cost of the liquid crystal display element.

Therefore, the liquid crystal display element manufactured by the method of this invention is superior to the liquid crystal display element known conventionally both in a performance point and a cost point, and can be applied suitably to various uses.

FIG. 1: is explanatory drawing which shows the pattern of the transparent conductive film in the liquid crystal cell 1 which has the patterned transparent conductive film manufactured by the Example and the comparative example.
FIG. 2: is explanatory drawing which shows the pattern of the transparent conductive film in the liquid crystal cell 2 which has the patterned transparent conductive film manufactured by the Example and the comparative example.

(Form to carry out invention)

<Polymer composition>

The polymer composition used in the method of the present invention,

(A) the following formula (A-I):

(In formula (AI), R is a hydrogen atom or a methyl group, and Y ¹ and Y ² are each independently an oxygen atom or a sulfur atom.)

A polymer having a group represented by the following (hereinafter also referred to as "polymer (A)"),

(C) organic solvent

It contains.

The polymer (A) in the polymer composition is preferably a (meth) acrylic polymer, and the polymer composition is preferably further

(B) It contains at least 1 sort (s) of polymer (henceforth "polymer (B)") chosen from the group which consists of polyamic acid, its imidation polymer, and polyorganosiloxane.

[Polymer (A)]

The polymer (A) used by this invention has group represented by said formula (AI). Y ¹ and Y ² in the formula (AI) are each preferably an oxygen atom.

It is preferable to contain the group represented by said formula (A-I) in 0.4-3.0 mmol / g, and, as for a polymer (A), it is more preferable to contain in 1.0-2.5 mmol / g.

In addition to the group represented by the above formula (A-I), the polymer (A) has the following formula (P):

(In formula (P), R ^I is a C4-C40 alkyl group or a C4-C40 fluoroalkyl group, or a C17-51 hydrocarbon group which has a steroid skeleton;

Z ^I is a single bond, ^* -O-, ^* -COO-, ^* -OCO- (wherein the bond at which "*" is attached is R ^I side),

R ^II is a cyclohexylene group or a phenylene group,

Z ^II is a single bond or ^* -(CH ₂ ) n _5- (wherein the bond to which "*" is attached is R ^I side and n5 is an integer of 1 to 5),

n1 is an integer of 1 to 5,

However, when n1 is two or more, two or more R <^II> and Z <^II> may mutually be same or different,

n2 is 0 or 1;

Z ^III is ^* -O-, ^* -COO- or ^* -OCO- (wherein the bond to which "*" is attached is the R ^I side),

n3 is an integer of 0 to 2,

n4 is 0 or 1)

It is preferable to further have group represented by.

As a C4-C40 alkyl group of R <^I> in said Formula (P), a C6-C40 alkyl group is preferable, Specifically, for example, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group A stearyl group;

As a C4-C40 fluoroalkyl group, a C4-C20 fluoroalkyl group is preferable, Specifically, a trifluoromethylpropyl group, a trifluoromethylbutyl group, a trifluoromethylhexyl group, a tri, Fluoromethyldecyl group, pentafluoroethylpropyl group, pentafluoroethylbutyl group, pentafluoroethyloctyl group, etc .;

As a 17-51 hydrocarbon group which has a steroid skeleton, a cholestanyl group, a cholesteryl group, a lanostanyl group, etc. are mentioned, for example.

It is preferable that the said alkyl group and the fluoroalkyl group are each a linear group.

It is preferable that the cyclohexylene group and the phenylene group of R <^II> in said Formula (P) are 1, 4- cyclohexylene group and 1, 4- phenylene group, respectively.

It is preferable that n1 in said Formula (P) is an integer of 1-4.

In the formula ^{(P) - (R Ⅱ -Z} Ⅱ) n1 - As the divalent group represented by, as if n1 is 1, for example, 1,4-phenylene, 1,4-cyclohexylene group, etc. of;

As n1 is 2, for example, a 4,4'-biphenylene group, a 4,4'-bicyclohexylene group, and a following formula:

(In the above formula, the bonding hand with "*" is the R ^I side.)

The group represented by each of;

When n1 is 3, the following formula:

(In the above formula, the bonding hand with "*" is the R ^I side.)

Such as represented by;

When n1 is 4, the following formula:

(In the above formula, the bonding hand with "*" is the R ^I side.)

The group etc. which are represented by these are mentioned as a preferable thing, respectively.

It is preferable that n3 in said Formula (P) is 2. Z ^Ⅱ is ^* - (CH _{2) n5} - that the n5 is 1 or 2. As the case is preferred.

It is preferable to contain the group represented by said formula (P) in 0.7 mmol / g or less, and, as for a polymer (A), it is more preferable to contain in 0.1-0.5 mmol / g.

It is preferable that the weight average molecular weight (henceforth "Mw") of polystyrene conversion measured by the gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) about a polymer (A) is 1,000-100,000, Furthermore, It is preferable that it is 3,000-50,000. Moreover, it is preferable that the number average molecular weight (henceforth "Mn") of polystyrene conversion measured on the same conditions is 700-80,000, Furthermore, it is preferable that it is 2,000-40,000.

It is preferable that a polymer (A) is a (meth) acrylic-type polymer. Here, "(meth) acrylic-type polymer" means the polymer which has a structural unit derived from at least 1 sort (s) chosen from the group which consists of acrylic acid, methacrylic acid, acrylic acid ester, and methacrylic acid ester.

The method for producing the polymer (A) is not particularly limited as long as it satisfies the above requirements, but for example, a polymer having a group Z ¹ ,

A compound having both a group represented by the formula (AI) and a group Z ² , or

It does not have a group represented by the formula (AI) group and a compound having both the group Z ² and the formula (AI) represented by the group in admixture with a compound having a Z ²

Wherein groups Z ¹ and Z ² are each groups to which they react to form a bond group

It can manufacture by reacting with. In this case, a polymer used as a raw material based polymer (A) having both a group represented by the group, and the formula (P) other than Z ¹ represented by the formula (AI) by as having airway represented by the above formula (P) Can be obtained.

Examples of the group Z ^1, for example, a carboxyl group, a hydroxyl group, an acid anhydride group, and the like. As the group Z ^2, Z ¹ group is an epoxy group when the carboxyl date;

When the group Z ¹ is a hydroxyl group, an isocyanate group;

When the group Z ¹ is an epoxy group, a carboxyl group;

When the group Z ¹ acid anhydride date is preferable that each hydroxyl group or an epoxy group.

Group includes (hereinafter referred to as a "polymer (b-1)") polymer having a carboxyl group as Z ^1, for example, polymerization having a carboxyl group polymerizable with the polymer, a carboxyl group of the unsaturated compound, unsaturated compound and other polymerizable unsaturated Copolymers with compounds, polyamic acid, partially imidized polymers of polyamic acid, and the like,

Since it is preferable that a polymer (A) is a (meth) acrylic-type polymer, the polymer (b-1) which is its precursor,

(Co) polymers of at least one polymerizable unsaturated compound selected from (meth) acrylic acid esters having (meth) acrylic acid and a carboxyl group, and

Copolymer of a polymerizable unsaturated compound having a carboxyl group with a (meth) acrylic acid ester having no carboxyl group

It is preferable that it is a (meth) acrylic-type polymer chosen from.

As a polymerizable unsaturated compound which has the said carboxyl group, For example, (meth) acrylic acid and maleic acid;

Unsaturated compounds obtained by adding (meth) acrylic acid and lactones; And

It is preferable to use 1 or more types chosen from the group which consists of an unsaturated compound obtained by adding hydroxyalkyl (meth) acrylate, a dibasic acid, or its anhydride. As said dibasic acid, succinic acid, maleic acid, phthalic acid etc. are mentioned, for example. Of these, at least one selected from the group consisting of (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid and ω-carboxypolycaprolactone mono (meth) acrylate is preferably used, and furthermore ( Meta) acrylic acid is preferred.

In the case where the polymer (b-1) is a copolymer of a polymerizable unsaturated compound having a carboxyl group and another polymerizable unsaturated compound, a polymerizable unsaturated compound having a group represented by the above formula (P) in part or all of the other polymerizable unsaturated compounds By setting it as a compound (henceforth "a compound (P)"), it can be set as the polymer which has both a carboxyl group and the group represented by said formula (P).

As said compound (P), it is preferable that it is (meth) acrylic acid ester which has group represented by said formula (P).

As such a compound (P), for example, cholestanyl acrylate, 4- (4'-n-propylbicyclohexyl-4-yl) phenyl methacrylate, 4- (4'-n-butylbicyclohexyl -4-yl) phenyl methacrylate, 4- (4'-n-pentylbicyclohexyl-4-yl) phenyl methacrylate, 4- (4'-n-hexylbicyclohexyl-4-yl) phenyl Methacrylate, 4- (4'-n-heptylbicyclohexyl-4-yl) phenylmethacrylate, 4- (4'-n-propylbicyclohexyl-4-yl) phenylacrylate, 4- ( 4'-n-butylbicyclohexyl-4-yl) phenylacrylate, 4- (4'-n-pentylbicyclohexyl-4-yl) phenylacrylate, 4- (4'-n-hexylbicyclo Hexyl-4-yl) phenylacrylate, 4- (4'-n-heptylbicyclohexyl-4-yl) phenylacrylate, 4- (4-n-heptylcyclohexyl) phenylmethacrylate, 4- ( 4-n-heptylcyclohexyl) phenylacrylate, 4- (4-n-propylcyclohexyl) phenylmethacrylate, 4- ( 4-n-propylcyclohexyl) phenylacrylate, 4- (4-n-butylcyclohexyl) phenylmethacrylate, 4- (4-n-butylcyclohexyl) phenylacrylate, 4- (4-n- Pentylcyclohexyl) phenyl methacrylate, 4- (4-n-pentylcyclohexyl) phenyl acrylate, 4- (4-n-hexylcyclohexyl) phenyl methacrylate, 4- (4-n-hexylcyclohexyl ) Phenyl acrylate, 4-dodecyl-phenyl methacrylate, 4-dodecylphenyl acrylate 4-octadecanyl-phenyl methacrylate, 4-octadecanylphenyl acrylate, cholestanyl methacrylate, etc. You can

In terms of vertical orientation, 4- (4'-n-pentylbicyclohexyl-4-yl) phenyl methacrylate, cholestanyl methacrylate, 4- (4'-n-pentylbicyclohexyl-4- It is especially preferable to use at least 1 sort (s) chosen from the group which consists of 1) phenyl acrylate and cholestanyl acrylate.

As a polymerizable unsaturated compound (henceforth "a compound (Q-1)") which does not have group represented by said formula (P), it is a (meth) acrylic acid ester, a vinyl aromatic compound, N-substituted maleimide, and a macro, for example. It is preferable to use at least 1 sort (s) chosen from the group which consists of a monomer (macromonomer),

Especially styrene, α-methylstyrene, acenaphthalene, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, N-cyclo It is preferable to use at least 1 sort (s) chosen from the group which consists of hexyl maleimide, N-benzyl maleimide, and N-phenyl maleimide.

As a use ratio of the polymerizable unsaturated compound which has a carboxyl group in manufacture of a polymer (b-1), it is preferable to set it as 4 weight% or more with respect to the total weight of all the polymerizable unsaturated compounds, and to set it as 5-50 weight%. It is more preferable, and it is preferable to set it as 10-40 weight% further. As a usage ratio of a compound (P), it is preferable to set it as 60 weight% or less with respect to the total of all the polymerizable unsaturated compounds, It is more preferable to set it as 5-50 weight%, Furthermore, it is set as 10-40 weight% desirable. As a usage ratio of a compound (Q-1), it is preferable to set it as 60 weight% or less with respect to the total weight of all the polymerizable unsaturated compounds, It is more preferable to set it as 5-50 weight%, Furthermore, to 10-40 weight% It is desirable to.

Production of the polymer (b-1) using the above-mentioned polymerizable unsaturated monomer can be performed by a well-known radical polymerization method.

When a polymer (b-1) is a polyamic acid or its partial imidation polymer, these can be manufactured similarly to the synthesis of the polyamic acid or its imidation polymer in the polymer (B) mentioned later, respectively. When using the polyimide partial imidation polymer as a polymer (b-1), in order to make the introduction ratio of the group represented by said formula (AI) into a desired value, it is preferable that the imidation ratio of a polymer shall be 50% or less. It is preferable and it is more preferable to set it as 30% or less. In the case where the partially imidized polymer of polyamic acid and polyamic acid has a group represented by the above formula (P), it is preferable to use the specific diamine described later in a range of 40 mol% or less with respect to the total diamine, and from 10 to 10 It is more preferable to use in 30 mol% of range.

The polymer (A) by reacting the polymer (b-1) obtained as described above with a compound having both of the group represented by the formula (AI) and the epoxy group (hereinafter referred to as "compound (c-1)"). Can be obtained.

The compound (c-1) used herein includes at least one selected from the group consisting of an unsaturated compound having a glycidyl group and a group represented by formula (AI) and an unsaturated compound having an alicyclic epoxy group and a group represented by formula (AI). It is preferable to use 1 type,

In particular, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, N- (3 , 5-dimethyl-4-glycidyl) benzylacrylamide, 4-hydroxybutyl (meth) acrylate glycidyl ether, p-vinylbenzyl glycidyl ether, 2- (2,3-epoxycyclopentyl) Ethyl (meth) acrylate, 2- (3,4-epoxycyclohexyl) ethyl (meth) acrylate and 2- (7,8-epoxy [tricyclo [5.2.1.0] dec-2-yl]) ethyl ( It is preferable to use at least 1 sort (s) chosen from the group which consists of a meta) acrylate.

As a use ratio of the compound (c-1) in reaction of a polymer (b-1) and a compound (c-1), it shall be 0.5-1.0 mol with respect to 1 mol of carboxyl groups which have a polymer (b-1). It is preferable to set it as 0.6-0.9 mol, and it is more preferable.

The reaction between the polymer (b-1) and the compound (c-1) is carried out in a suitable solvent, if necessary, preferably in the presence of a catalyst.

As a solvent used here, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, methoxy butyl acetate, a propylene glycol monomethyl ether acetate, etc. are mentioned, for example. Can be. The use ratio of the solvent refers to the ratio of the solid content concentration (the total weight of components other than the solvent in the reaction solution to the total weight of the reaction solution. The same applies in the description of the polymer (A)) to 20 to 60 weight. It is preferable to set it as the ratio used as%.

As a catalyst used, a tertiary amine, a quaternary ammonium salt, an alkylurea, an imidazole compound, etc. are mentioned, for example. As these specific examples, For example, dimethylbenzylamine etc. are mentioned as said tertiary amine;

Examples of the quaternary ammonium salts include tetrabutylammonium bromide, tetrabutylphosphonium chloride, tetraphenylphosphonium bromide, hexamethylphosphorotriamide and the like;

Examples of the alkylurea include 3- (3 ', 4'-dichlorophenyl) -1,1-dimethylurea;

As said imidazole compound, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecyl imidazole, 2-phenylimidazole, etc. are mentioned, respectively. It is preferable that the usage ratio of a catalyst shall be 0.001-10 weight part with respect to a total of 100 weight part of a polymer (b-1) and a compound (c-1).

The reaction temperature is preferably 70 to 110 ° C, more preferably 75 to 90 ° C.

The reaction time is preferably 2 to 15 hours, more preferably 5 to 10 hours.

As the polymer (hereinafter referred to as "polymer (b-2)") having a hydroxyl group as the group Z ^1, for example, polymerization having hydroxyl groups polymerizable with the polymer, the hydroxyl group of the unsaturated compound, unsaturated compound and other polymerizable unsaturated The copolymer with a compound, etc. are mentioned.

As a polymerizable unsaturated compound which has the said hydroxyl group, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerol mono (meth), for example In addition to the hydroxyalkyl (meth) acrylates, such as an acrylate, N-methylol acrylamide, allyl alcohol, etc. are mentioned, It is preferable to use 1 or more types chosen from these.

In the case where the polymer (b-2) is a copolymer of a polymerizable unsaturated compound having a hydroxyl group and another polymerizable unsaturated compound, a polymerizable unsaturated compound having a group represented by the above formula (P) in part or all of the other polymerizable unsaturated compounds By setting it as a compound, it can be set as the polymer which has both a hydroxyl group and the group represented by said formula (P). Here, as the polymerizable unsaturated compound having a group represented by the formula (P), the same compounds as those of the compound (P) described above can be used.

As another polymerizable unsaturated compound (henceforth a "compound (Q-2)") which does not have group represented by said formula (P) used for manufacture of a polymer (b-2), it is a hydroxyl group and said formula (P). It is preferable to use at least 1 sort (s) chosen from the group which consists of a (meth) acrylic acid ester, a vinyl aromatic compound, N-substituted maleimide, and a macromonomer which do not have both of the groups represented by

Especially styrene, α-methylstyrene, acenaphthylene, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, ethylene oxide modified (meth) acrylic of paracumylphenol It is preferable to use at least 1 sort (s) chosen from the group which consists of a rate, N-cyclohexyl maleimide, N-benzyl maleimide, and N-phenyl maleimide.

As a use ratio of the polymerizable unsaturated compound which has a hydroxyl group in manufacture of a polymer (b-2), it is preferable to set it as 20 weight% or more with respect to the total weight of all the polymerizable unsaturated compounds, and set it as 30 to 80 weight%. It is more preferable, and further it is preferable to set it as 40 to 70 weight%. As a usage ratio of a compound (P), it is preferable to set it as 60 weight% or less with respect to the total weight of all the polymerizable unsaturated compounds, It is more preferable to set it as 5-50 weight%, Furthermore, to set it as 10-40 weight% desirable. As a usage ratio of a compound (Q-2), it is preferable to set it as 70 weight% or less with respect to the total weight of all the polymerizable unsaturated compounds, It is more preferable to set it as 5 to 60 weight%, Furthermore, to 10-50 weight% It is desirable to.

Production of the polymer (b-2) using the above-mentioned polymerizable unsaturated monomer can be performed by a well-known radical polymerization method.

The polymer (A) by reacting the polymer (b-2) obtained as described above with a compound having both of the group represented by the formula (AI) and the isocyanate group (hereinafter referred to as "compound (c-2)"). ) Can be obtained.

As a compound (c-2) used here, 2- (meth) acryloyloxyethyl isocyanate, 2- (2-isocyanate ethoxy) ethyl (meth) acrylic acid, 1,1- (bisacrylo), for example Monooxymethyl) ethyl isocyanate, etc. are mentioned.

As a usage ratio of the compound (c-2) in reaction of a polymer (b-2) and a compound (c-2), it is preferable to set it as 0.4-0.9 mol with respect to 1 mol of hydroxyl groups which a polymer (b-2) has, It is more preferable to set it as 0.5-0.8 mol.

Reaction of a polymer (b-2) and a compound (c-2) is performed in a suitable solvent as needed, Preferably it is carried out in presence of a catalyst.

As a solvent used here, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, methoxy butyl acetate, a propylene glycol monomethyl ether acetate, etc. are mentioned, for example. Can be. It is preferable to make into the ratio which the use ratio of a solvent become 20 to 60 weight% of solid content concentration of a reaction solution.

As a catalyst used, an amine compound, an organometallic compound, etc. are mentioned, for example. As said amine compound, For example, triethylamine, tripropylamine, triethylenediamine, diazabicyclo undecene, etc .;

Examples of the organometallic compound include tin octylate, dibutyltin diacetate, dibutyltin dilaurate, bismuth octylate and bismuth decanoate, respectively. When using a catalyst, it is preferable that the use ratio shall be 0.001-2 weight part with respect to a total of 100 weight part of a polymer (b-2) and a compound (c-2).

The reaction temperature is preferably 70 to 110 ° C, more preferably 75 to 90 ° C.

The reaction time is preferably 2 to 15 hours, more preferably 5 to 10 hours.

As the polymer (hereinafter referred to as a "polymer (b-3)") having an epoxy group as the group Z ^1, for example polymerization with an epoxy group polymerizable with the polymer, the epoxy group of the unsaturated compound, unsaturated compound and other polymerizable unsaturated The copolymer with a compound, an epoxy resin, etc. are mentioned.

As a polymerizable unsaturated compound which has the said epoxy group, it is preferable to use at least 1 sort (s) chosen from the group which consists of a (meth) acrylic acid ester which has an epoxy group, and a styrene derivative which has an epoxy group,

Especially glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Dilether, o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, p-vinylbenzylglycidylether, 2,4-diglycidyloxymethylstyrene and 3,4,5-triglycidyl It is preferable to use at least 1 sort (s) chosen from the group which consists of dilmethylstyrene.

In the case where the polymer (b-3) is a copolymer of a polymerizable unsaturated compound having an epoxy group with another polymerizable unsaturated compound, a polymerizable unsaturated compound having a group represented by the above formula (P) in part or all of the other polymerizable unsaturated compounds By setting it as a compound, it can be set as the polymer which has both an epoxy group and the group represented by said formula (P). Here, as the polymerizable unsaturated compound having a group represented by the formula (P), the same compounds as those of the compound (P) described above can be used.

As another polymerizable unsaturated compound (henceforth a "compound (Q-3)") which does not have group represented by said formula (P) used for manufacture of a polymer (b-3), it is (meth) acrylic acid ester and vinyl It is preferable to use at least 1 sort (s) chosen from the group which consists of an aromatic compound, N-substituted maleimide, and a macromonomer,

Especially styrene, α-methylstyrene, acenaphthylene, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobor Nyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, N-cyclohexylmaleimide, N- It is preferable to use at least 1 sort (s) chosen from the group which consists of benzyl maleimide and N-phenyl maleimide.

As a use ratio of the polymerizable unsaturated compound which has an epoxy group in manufacture of a polymer (b-3), it is preferable to set it as 20 weight% or more with respect to the total weight of all the polymerizable unsaturated compounds, and to make it 30 to 90 weight% It is more preferable, and also it is preferable to set it as 40 to 75 weight% further. As a usage ratio of a compound (P), it is preferable to set it as 60 weight% or less with respect to the total weight of all the polymerizable unsaturated compounds, It is more preferable to set it as 5-50 weight%, Furthermore, to set it as 10-40 weight% desirable. As a usage ratio of a compound (Q-3), it is preferable to set it as 60 weight% or less with respect to the total weight of all the polymerizable unsaturated compounds, It is more preferable to set it as 5-50 weight%, Furthermore, as 5-40 weight% It is desirable to.

Production of the polymer (b-3) using the above-mentioned polymerizable unsaturated monomer can be performed by a well-known radical polymerization method.

In the case where the polymer (b-3) is an epoxy resin, such a polymer (b-3) may be, for example, reacted with an alcoholic hydroxyl group and epichlorohydrin of a bisphenol A type epoxy resin or a bisphenol A type epoxy resin. Epoxy resin, bisphenol S-type epoxy resin, biphenyl glycidyl ether, phenol novolak type obtained by reaction of an alcoholic hydroxyl group and epichlorohydrin of an epoxy resin, bisphenol F-type epoxy resin, bisphenol F-type epoxy resin Epoxy resin, cresol novolak-type epoxy resin, triglycidyl isocyanurate, trisphenol methane type epoxy resin, fluorene epoxy resin, alicyclic epoxy resin, dicyclopentadiene type epoxy resin, In addition, copolymerization Type epoxy resin can be used.

The polymer (b-3) obtained or prepared as mentioned above is made to react with the compound which has both a group represented by said formula (AI), and a carboxyl group (henceforth a "compound (c-3)"), and a polymer (A) can be obtained.

As a compound (c-3) used here, (meth) acrylic acid, (omega)-carboxy- polycaprolactone mono (meth) acrylate, 2- (meth) acryloyl ethyl succinic acid, etc. are mentioned, for example.

As a usage ratio of the compound (c-3) in reaction of a polymer (b-3) and a compound (c-3), it is preferable to set it as 0.2-1.0 mol with respect to 1 mol of epoxy groups which a polymer (b-3) has. More preferably 0.4 to 0.9 mol.

The reaction between the polymer (b-3) and the compound (c-3) is carried out in a suitable solvent, if necessary, preferably in the presence of a catalyst.

As a solvent used here, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, methoxy butyl acetate, a propylene glycol monomethyl ether acetate, etc. are mentioned, for example. Can be. It is preferable to make into the ratio which the use ratio of a solvent become 20 to 60 weight% of solid content concentration of a reaction solution.

As a catalyst used, a tertiary amine, a quaternary ammonium salt, an alkylurea, an imidazole compound, etc. are mentioned, for example. As these specific examples, For example, dimethylbenzylamine etc. are mentioned as said tertiary amine;

Examples of the quaternary ammonium salts include tetrabutylammonium bromide, tetrabutylphosphonium chloride, tetraphenylphosphonium bromide, hexamethylphosphorotriamide and the like;

Examples of the alkylurea include 3- (3 ', 4'-dichlorophenyl) -1,1-dimethylurea;

As said imidazole compound, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecyl imidazole, 2-phenylimidazole, etc. are mentioned, respectively. It is preferable that the use ratio of a catalyst shall be 0.001-10 weight part with respect to a total of 100 weight part of a polymer (b-3) and a compound (c-3).

The reaction temperature is preferably 70 to 110 ° C, more preferably 75 to 90 ° C.

The reaction time is preferably 2 to 15 hours, more preferably 5 to 10 hours.

Group (hereinafter referred to as "polymer (b-4)") polymer having an acid anhydride group as Z ¹ Examples of such polymeric other unsaturated compounds and those having a polymer, an acid anhydride of the polymerizable unsaturated compound such having an acid anhydride The copolymer with a polymerizable unsaturated compound, etc. are mentioned.

Examples of the polymerizable unsaturated compound having an anhydride group include maleic anhydride, methyl maleic anhydride, tetrahydro phthalic anhydride, methyltetrahydro phthalic anhydride, methylnadic acid and the like.

In the case where the polymer (b-4) is a copolymer of a polymerizable unsaturated compound having an acid anhydride group with another polymerizable unsaturated compound, a polymerizable polymer having a group represented by the above formula (P) in which part or all of the other polymerizable unsaturated compounds are represented By setting it as an unsaturated compound, it can be set as the polymer which has both an acid anhydride group and the group represented by said formula (P). Here, as the polymerizable unsaturated compound having a group represented by the formula (P), the same compounds as those of the compound (P) described above can be used.

As another polymerizable unsaturated compound which does not have group represented by said formula (P) used for manufacture of a polymer (b-4), the thing similar to said compound (Q-1) can be used.

As a use ratio of the polymerizable unsaturated compound which has an acid anhydride group in manufacture of a polymer (b-4), it is preferable to set it as 20 weight% or more with respect to the total weight of all the polymerizable unsaturated compounds, and it is 30-80 weight% More preferably, it is more preferable to set it as 40 to 70 weight%. As a usage ratio of a compound (P), it is preferable to set it as 60 weight% or less with respect to the total weight of all the polymerizable unsaturated compounds, It is more preferable to set it as 5-50 weight%, Furthermore, it is preferable to set it as 10-40 weight% Do. As a usage ratio of a compound (Q-1), it is preferable to set it as 70 weight% or less with respect to the total weight of all the polymerizable unsaturated compounds, It is more preferable to set it as 5 to 60 weight%, Furthermore, to 10-50 weight% It is desirable to.

Production of the polymer (b-4) using the above-mentioned polymerizable unsaturated monomer can be performed by a well-known radical polymerization method.

The compound (b-4) obtained as described above has a compound (hereinafter referred to as "compound (c-4)") having the both of the group represented by the formula (AI) and the hydroxyl group as the group Z ² (hereinafter referred to as "compound (c-4)") or the formula ( by AI) reaction with a compound having a group and a group represented by both the epoxy group as Z ^2, it is possible to obtain the polymer (a). Hereinafter, it demonstrates dividing into the case where group Z <^2> is a hydroxyl group and an epoxy group.

Group The compound (c-4) used in the case where Z ² is a hydroxyl group includes, for example, hydroxyalkyl (meth) acrylate, N- methylol acrylamide, allyl alcohol, and the like.

As a use ratio of the compound (c-4) in reaction of a polymer (b-4) and a compound (c-4), it shall be 0.2-1.0 mol with respect to 1 mol of acid anhydride groups which have a polymer (b-4). It is preferable to set it as 0.4-0.9 mol.

The reaction between the polymer (b-4) and the compound (c-4) is carried out in a suitable solvent, if necessary, preferably in the presence of a catalyst.

As a solvent used here, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, methoxy butyl acetate, a propylene glycol monomethyl ether acetate, etc. are mentioned, for example. Can be. It is preferable to make into the ratio which the use ratio of a solvent become 20 to 60 weight% of solid content concentration of a reaction solution.

As a catalyst used, an imidazole compound is mentioned, for example, As a specific example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimidazole etc. are mentioned. It is preferable that the use ratio of a catalyst shall be 0.001-1 weight part with respect to a total of 100 weight part of a polymer (b-4) and a compound (c-4).

Reaction temperature becomes like this. Preferably it is 70-110 degreeC, More preferably, it is 75-90 degreeC.

The reaction time is preferably 2 to 15 hours, more preferably 5 to 10 hours.

Meanwhile, the group includes compounds having both the group and an epoxy group represented by the formula (AI) used in the case where Z ² is an epoxy group, may be the same as the above compound (c-1).

As a use ratio of the compound (c-1) in reaction of a polymer (b-4) and a compound (c-1), it is 0.3-1.0 mol with respect to 1 mol of acid anhydride groups which a polymer (b-4) has. It is preferable to set it as 0.4-0.9 mol, and it is more preferable.

The reaction between the polymer (b-4) and the compound (c-1) is carried out in a suitable solvent, if necessary, preferably in the presence of a catalyst.

As a solvent used here, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, methoxy butyl acetate, a propylene glycol monomethyl ether acetate, etc. are mentioned, for example. Can be. It is preferable to make into the ratio which the use ratio of a solvent become 20 to 60 weight% of solid content concentration of a reaction solution.

As a catalyst used, an imidazole compound is mentioned, for example, As a specific example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimidazole etc. are mentioned. It is preferable that the use ratio of a catalyst shall be 0.001-2 weight part with respect to a total of 100 weight part of a polymer (b-4) and a compound (c-1).

The reaction temperature is preferably 70 to 110 ° C, more preferably 75 to 90 ° C.

The reaction time is preferably 2 to 15 hours, more preferably 5 to 10 hours.

The polymer (A) produced in this way can be used individually or in mixture of 2 or more types.

[Polymer (B)]

The polymer (B) used arbitrarily in this invention is at least 1 sort (s) of polymer chosen from the group which consists of polyamic acid, its imidation polymer, and polysiloxane. The polymer (B) preferably does not have a group represented by the formula (A-I). The polymer (B) may have a group represented by the formula (P).

Polyamic acid and imidized polymers thereof

The said polyamic acid can be synthesize | combined, for example by making tetracarboxylic dianhydride and diamine react. Tetracarboxylic dianhydride and diamine used here preferably do not have the group represented by said formula (A-I), respectively. The said imidation polymer can be synthesize | combined by dehydrating and ring-closing the said polyamic acid.

{Tetracarboxylic dianhydride}

As tetracarboxylic dianhydride used for synthesize | combining the said polyamic acid, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. As these specific examples, As an aliphatic tetracarboxylic dianhydride, For example, butanetetracarboxylic dianhydride etc .;

As alicyclic tetracarboxylic dianhydride, For example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5- tricarboxy cyclopentyl acetic dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4 , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3- Oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3 -Furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornan-2: 3,5: 6-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone and the like;

As aromatic tetracarboxylic dianhydride, a pyromellitic dianhydride etc. can be mentioned, respectively, For example, In addition, you may use the tetracarboxylic dianhydride of patent document 1 (Unexamined-Japanese-Patent No. 2010-97188).

As tetracarboxylic dianhydride used for synthesize | combining the said polyamic acid, among these, using only alicyclic tetracarboxylic dianhydride or using a mixture of alicyclic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride is used. desirable. In the latter case, the ratio of the alicyclic tetracarboxylic dianhydride in the total tetracarboxylic dianhydride is preferably 20 mol% or more, more preferably 40 mol% or more.

{Diamine}

As a diamine used for synthesize | combining the said polyamic acid, it is preferable to use the diamine containing the diamine (henceforth "specific diamine") which has group represented by said formula (P). Thereby, the polyamic acid obtained and its imidation polymer can be made to have group represented by said formula (P).

The group represented by the formula (P) in the specific diamine is preferably a group in which Z ^II is a single bond and n1 is 1 or 2. It is more preferable that n1 is 1.

As a specific diamine in this invention, it is preferable that it is aromatic diamine which has group represented by said formula (P), As a specific example, dodecaneoxy-2, 4- diamino benzene, pentadecaneoxy-2, 4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecaneoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, pentadecaneoxy-2,5- Diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5- Diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid ranostanyl, and the like. It is preferable to use. Specific diamines in the present invention are, in particular, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene and cholesteryl It is preferable to use at least 1 sort (s) chosen from the group which consists of oxy-3, 5- diamino benzene.

As a diamine used for synthesize | combining the said polyamic acid, only the specific diamine mentioned above may be used, and a specific diamine and other diamine may be used together.

Other diamine which can be used here is diamine which does not have group represented by said formula (P), For example, it does not correspond to the said specific diamine as aliphatic diamine, alicyclic diamine, aromatic diamine, diamino organosiloxane, etc. will be. As these specific examples, As an aliphatic diamine, For example, 1, 1- metha xylylenediamine, 1, 3- propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, etc .;

As alicyclic diamine, For example, 1, 4- diamino cyclohexane, 4, 4'- methylenebis (cyclohexylamine), 1, 3-bis (aminomethyl) cyclohexane, etc .;

As aromatic diamine, for example, p-phenylenediamine, 4,4'- diaminodiphenylmethane, 4,4'- diaminodiphenyl sulfide, 1,5- diaminonaphthalene, 2,2'-dimethyl -4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4'-diamino Diphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy Phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m- Phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4 -Diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3 , 6-diaminocarbazole, N-fe Benzidine and the like, N, N'- bis (4-aminophenyl) -N, N'- dimethyl benzidine-3,6-diamino-carbazole, N, N'- bis (4-aminophenyl);

Examples of the diaminoorganosiloxanes include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like, and are described in Patent Document 1 (Japanese Patent Laid-Open No. 2010-97188). You may use diamine.

As diamine used for synthesize | combining the said polyamic acid, it is preferable to contain 2 mol% or more of said specific diamine with respect to all diamine, It is more preferable to contain 2 to 60 mol%, It is more preferable that it is 5-40 mol% It is more preferable to contain, and it is preferable to contain especially 10-30 mol%.

{Molecular weight regulator}

When synthesize | combining the said polyamic acid, you may make it synthesize | combine a terminal-modified polymer using a suitable molecular weight modifier with tetracarboxylic dianhydride and diamine as mentioned above. By setting it as such a terminal modified polymer, the coating property (printability) of a polymer composition can be improved, without impairing the effect of this invention.

As said molecular weight modifier, an acid monoanhydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned, for example. As these specific examples, as acid monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride My back;

As a monoamine compound, For example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, etc .;

As a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, respectively.

It is preferable to make the use ratio of a molecular weight modifier into 10 weight part or less with respect to a total of 100 weight part of tetracarboxylic dianhydride and diamine to be used.

{Synthesis of Polyamic Acid}

The use ratio of tetracarboxylic dianhydride and diamine to be used for the polyamic acid synthesis reaction is preferably a ratio in which the acid anhydride group of tetracarboxylic dianhydride is 0.2 to 2 equivalents to 1 equivalent of the amino group of the diamine. The ratio is 0.3 to 1.2 equivalents.

Synthesis reaction of polyamic acid, Preferably in an organic solvent, Preferably it is -20 degreeC-150 degreeC, More preferably, it is 0-100 degreeC, Preferably it is 0.1-24 hours, More preferably, it is 0.5-12 Time is done.

As the organic solvent, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexa Non-protic polar solvents such as methyl phosphotriamide;

Phenolic solvents, such as m-cresol, a xylenol, a phenol, and a halogenated phenol, are mentioned. It is preferable that the usage-amount (a) of an organic solvent is an amount so that the total amount (b) of tetracarboxylic dianhydride and diamine may be 0.1-30 weight% with respect to the total amount (a + b) of a reaction solution.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained.

This reaction solution may be used as it is for preparation of a polymer composition, may be used to prepare a polymer composition after isolating polyamic acid contained in the reaction solution, or may be used to prepare a polymer composition after purifying the isolated polyamic acid. good. In the case where the polyamic acid is dehydrated and closed to give an imidized polymer, the reaction solution may be used as it is for dehydration ring closure, or after isolation of the polyamic acid contained in the reaction solution, or may be used for dehydration ring closure. After refine | purifying an acid, you may provide for dehydration ring-closure reaction. Isolation and purification of polyamic acid can be performed according to a well-known method.

{Synthesis of imidized polymer}

The said imidation polymer can be obtained by dehydrating and ring-closing the polyamic acid synthesize | combined as mentioned above and imidating.

The imidation polymer in this invention may be the complete imide which dehydrated and closed all the dark acid structures which the polyamic acid which is its precursor has, and dehydrates and rings only a part of the dark acid structure, and a dark acid structure and an imide ring structure coexist. A partial imide may be sufficient. It is preferable that the imidation ratio of the imidation polymer in this invention is 40% or more. This imidation ratio shows the ratio which the number of the imide ring structure to the sum of the number of the dark acid structures of the imidation polymer, and the number of imide ring structures occupies as a percentage.

The dehydration ring closure of polyamic acid is preferably carried out by a method of heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating it as necessary. . Among these, it is preferable by the latter method.

In the method of adding a dehydrating agent and a dehydrating ring-closure catalyst in the solution of the polyamic acid, for example, acid anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride can be used as the dehydrating agent. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of the dark acid structure of polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. As an organic solvent used for a dehydration ring-closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid is mentioned. The reaction temperature of the dehydration ring-closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

In this way, a reaction solution containing a polyimide is obtained. This reaction solution may be provided as it is to preparation of a polymer composition as it is, may be provided to preparation of a polymer composition after removing a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, or may be provided to preparation of a polymer composition after isolation of a polyimide. Alternatively, the isolated polyimide may be purified and then used for preparation of the polymer composition. These purification operations can be performed according to a well-known method.

[Polyorganosiloxane]

It is preferable that the said polyorganosiloxane has group represented by said formula (P), and can contain this group in 0.01 mol / g or less range. As a ratio of the group represented by said Formula (P) which the said polyorganosiloxane has, it is preferable that it is 0.0001-0.005 mol / g, and it is more preferable that it is 0.0002-0.002 mol / g.

It is preferable that the weight average molecular weight Mw of polystyrene conversion measured by the gel permeation chromatography about the said polyorganosiloxane is 500-1,000,000, It is more preferable that it is 1,000-100,000, Furthermore, it is preferable that it is 1,000-50,000. .

The polyorganosiloxane may be produced by any method, but for example, an alkoxysilane compound, preferably a silane compound having a group represented by the formula (P) and an alkoxyl group (hereinafter referred to as "silane compound (a1) Or a mixture of a silane compound (a1) and another alkoxysilane compound (hereinafter referred to as "silane compound (a2)"),

A method of reacting in the presence of dicarboxylic acid and alcohol (manufacturing method 1), or a method of hydrolysis and condensation (manufacturing method 2), or

A silane compound having an epoxy group and an alkoxyl group (hereinafter referred to as "silane compound (a2-1)") or alkoxysilane compound different from the silane compound (a2-1) (hereinafter referred to as "silane compound (a2-2)"). Mixture),

After reacting in the presence of dicarboxylic acid and alcohol, it is further reacted with a compound having a group represented by the formula (P) and a carboxyl group (hereinafter referred to as "specific carbonic acid") (Manufacturing method 3), or

It can manufacture by the method (manufacturing method 4) which makes it react with specific carbonic acid further after hydrolysis and condensation.

The silane compounds (a2-1) and (a2-2) preferably do not each have a group represented by the formula (AI), and in this case, the aggregate of the silane compounds (a2-1) and (a2-2) together is It is consistent with the range of the silane compound (a2). Moreover, it is preferable that the said silane compounds (a1), (a2-1), and (a2-3) do not have group represented by said formula (A-I).

As said silane compound (a1), following formula (a1-1):

(Formula (a1-1), and of, R ^I, R ^Ⅱ, Z ^I, Z ^Ⅱ, Z ^Ⅲ, n1, n2, n3 and n4 are the same meaning as in the formula (P), respectively,

R ¹ is a phenyl group or an alkyl group having 1 to 12 carbon atoms or an alkylphenyl group having an alkyl group having 1 to 12 carbon atoms,

n is an integer of 1 to 3)

The compound represented by is mentioned. It is preferable that n in Formula (a1-1) is 1.

As a specific example of such a silane compound (a1), for example, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-i-propoxysilane , n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-n-pentasilane, n-butyltri-sec-butoxysilane, n-butyltriphenoxy Cysilane, n-butyltri-p-methylphenoxy silane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, n-pentyltri-n-propoxysilane, n-pentyltri-i -Propoxysilane, n-pentyltri-n-butoxysilane, n-pentyltri-sec-butoxysilane, n-pentyltri-n-penttaxysilane, n-pentyltri-sec-part Methoxysilane, n-pentyltriphenoxysilane, n-pentyltri-p-methylphenoxysilane, 2- (perfluoro-n-hexyl) ethyltrimethoxysilane, 2- (perfluoro-n -Hexyl) ethyltriethoxysilane, 2- (perfluoro-n-hexyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-i-propoxysil , 2- (perfluoro-n-hexyl) ethyl tri-n-butoxysilane, 2- (perfluoro-n-hexyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n- Octyl) ethyltrimethoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane, 2- (perfluoro-n-octyl) ethyltri-n-propoxysilane, 2- (perfluoro Rho-n-octyl) ethyltri-i-propoxysilane, 2- (perfluoro-n-octyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-octyl) ethyltri-sec -Butoxysilane, n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane, n-dodecyltri-n-propoxysilane, n-dodecyltri-i-propoxysilane, n-dode Siltri-n-butoxysilane, n-dodecyl tri-sec-butoxysilane, etc. are mentioned, One or more types selected from these can be used.

As said silane compound (a2-1), for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3 -Glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, etc. can be mentioned, One or more types selected from these can be used.

The said silane compound (a2-2), Preferably it is an alkoxysilane compound other than the said silane compound (a1) and a silane compound (a2-1), For example, Preferably, it is a following formula (a2-2-1):

(R ² ) _m Si (OR ³ ) _4-m (a2-2-1)

(In formula (a2-2-1), R <^2> is a C1-C3 alkyl group, a C1-C3 fluoroalkyl group, or a phenyl group, or an alkylphenyl group which has a C1-C3 alkyl group,

R ³ is a phenyl group or an alkyl group having 1 to 12 carbon atoms, or an alkylphenyl group having an alkyl group having 1 to 12 carbon atoms,

m is an integer of 0 to 3)

The compound represented by is mentioned.

As a compound represented by said formula (a2-2-1), for example, ethyl trimethoxysilane, ethyl triethoxysilane, methyl trimethoxysilane, methyl triethoxysilane, tetramethoxysilane, and tetraethoxysilane It is preferable to use 1 or more types chosen from the group which consists of, and it is especially preferable to use 1 or more types chosen from the group which consists of tetramethoxysilane and tetraethoxysilane.

The use ratio with respect to all the silane compounds of each silane compound used as a raw material at the time of manufacturing the polyorganosiloxane in this invention is as follows according to the manufacturing method of a polyorganosiloxane.

(1) the preparation of polyorganosiloxane by preparation method 1 or 2;

Silane compound (a1): Preferably it is 1 mol% or more, More preferably, it is 2-40 mol%, More preferably, it is 5-20 mol%

Silane compound (a2): Preferably it is 99 mol% or less, More preferably, it is 60-98 mol%, More preferably, it is 80-95 mol%

(2) the preparation of polyorganosiloxanes according to preparation 3 or 4;

Silane compound (a2-1): Preferably it is 50 mol% or more, More preferably, it is 60-100 mol%, More preferably, it is 80-100 mol%

Silane compound (a2-2): Preferably it is 50 mol% or less, More preferably, it is 0-40 mol%, More preferably, it is 0-20 mol%

Hereinafter, the method of making the silane compound reacted in manufacture methods 1 and 3 in presence of dicarboxylic acid and alcohol is demonstrated.

Examples of the dicarboxylic acid used herein include oxalic acid, malonic acid, a compound in which two carboxyl groups are bonded to an alkylene group having 2 to 4 carbon atoms, benzenedicarboxylic acid, and the like. Specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, etc. are mentioned, It is preferable to use 1 or more types selected from these. Particularly preferably oxalic acid.

It is preferable that the use ratio of dicarboxylic acid is made into the quantity which becomes 0.2-2.0 mol, and the quantity of carboxyl group with respect to a total of 1 mol of alkoxyl groups which the silane compound used as a raw material is made into 0.5-1.5 mol. More preferred.

As said alcohol, a primary alcohol can be used suitably, It is preferable to use a C1-C4 aliphatic primary alcohol, and methanol, ethanol, i-propanol, n-propanol, i-butanol, sec-butanol And it is more preferable to use 1 or more types chosen from the group which consists of t-butanol, and it is especially preferable to use 1 or more types chosen from the group which consists of methanol and ethanol.

It is preferable to make into the ratio which the ratio of the silane compound and dicarboxylic acid which occupy the whole amount of the reaction solution to become 3 to 80 weight%, and the use ratio of the alcohol in the manufacturing methods 1 and 3 becomes 25 to 70 weight% It is more preferable to set it as a ratio.

It is preferable to make reaction temperature into 1-100 degreeC, More preferably, it is 15-80 degreeC.

The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 8 hours.

In the reaction of the silane compounds of Production Methods 1 and 3, it is preferable not to use any solvent other than the above alcohols.

In the above production method, it is estimated that the polyorganosiloxane which is the (co) condensate of a silane compound produces | generates by alcohol acting on the intermediate produced | generated by reaction of a silane compound and dicarboxylic acid.

Next, the hydrolysis and condensation reaction of the silane compound performed in Production Methods 2 and 4 will be described.

This hydrolysis-condensation reaction can be performed by making a silane compound and water react in the presence of a catalyst, Preferably in a suitable organic solvent.

The ratio of water used here is an amount with respect to the total of 1 mol of the alkoxyl groups which the silane compound used as a raw material has, and it is preferable to set it as 0.5-2.5 mol.

As said catalyst, an acid, a base, a metal compound, etc. are mentioned. As an example of such a catalyst, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid, etc. are mentioned, for example.

As the base, any of an inorganic base and an organic base can be used, and examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like;

Examples of the organic base include tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butyl amine, pyridine and 4-dimethylaminopyridine; Tetramethylammonium hydroxide, and the like.

As a metal compound, a titanium compound, a zirconium compound, etc. are mentioned, for example.

It is preferable to set it as 10 weight part or less with respect to a total of 100 weight part of the silane compound used as a raw material, It is more preferable to set it as 0.001-10 weight part, Furthermore, it is preferable to set it as 0.001-1 weight part. .

As said organic solvent, alcohol, ketone, an amide, ester, and other aprotic compounds are mentioned, for example. As said alcohol, all of the partial ester of the alcohol which has one hydroxyl group, the alcohol which has two or more hydroxyl groups, and the alcohol which has two or more hydroxyl groups can be used. As the ketone, monoketone and β-diketone can be preferably used. Of these, it is preferable to use partial esters of alcohols having a plurality of hydroxyl groups, and in particular, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether , Propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, etc. can be illustrated preferably, It is especially preferable to use 1 or more types chosen from these.

As a usage ratio of an organic solvent, it is preferable to set it as the ratio which becomes 1 to 90 weight% as a ratio which the total weight of components other than the organic solvent in a reaction solution occupies for the total amount of reaction solution, and becomes 10 to 70 weight% It is more preferable to set it as a ratio.

The water added at the time of the hydrolysis-condensation reaction of a silane compound can be added intermittently or continuously in the silane compound which is a raw material, or in the solution which melt | dissolved a silane compound in the organic solvent.

The catalyst may be added in advance in the silane compound as a raw material or in a solution in which the silane compound is dissolved in an organic solvent, or may be dissolved or dispersed in water to be added.

It is preferable to make reaction temperature into 1-100 degreeC, More preferably, it is 15-80 degreeC.

The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 8 hours.

In the manufacturing methods 1 and 2 by the above means, the polyorganosiloxane which can be contained in the polymer composition in this invention is obtained directly;

On the other hand, in manufacturing methods 3 and 4, the polyorganosiloxane which has an epoxy group which is a precursor of polyorganosiloxane is obtained. In the manufacturing methods 3 and 4, (A) polyorganosiloxane contained in the polymer composition in this invention can be obtained by making the polyorganosiloxane which has this epoxy group react with specific carbonic acid further.

The specific carboxylic acid used herein is a compound having a group represented by the formula (P) and a carboxyl group. As a specific carbonic acid, it is following formula (C-1):

(In formula (C-1), R ^I , R ^II , Z ^I , Z ^II , Z ^III , n1, n2, n3 and n4 have the same meanings as those in the formula (P).)

The compound represented by is mentioned. As a specific example of a compound represented by said formula (C-1), for example, valeric acid, caproic acid, caprylic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, 4- (n-pentyl) benzoic acid, 4- (n -Hexyl) benzoic acid, 4- (n-heptyl) benzoic acid, 4- (n-octyl) benzoic acid, 4- (n-nonyl) benzoic acid, 4- (n-decyl) benzoic acid, 4- (n-dodecyl) benzoic acid , 4- (n-octadecyl) benzoic acid, 4- (4-pentyl-cyclohexyl) -benzoic acid, 4- (4-heptyl-cyclohexyl) -benzoic acid, and the like, and one or more selected from these. Can be used.

It is preferable to use the specific carbonic acid used for reaction with the polyorganosiloxane which has an epoxy group as 5-50 mol with respect to 1 mol of epoxy groups which precursor polyorganosiloxane has, and it is more preferable to set it as 10-40 mol. Do.

The reaction between the polyorganosiloxane having an epoxy group and the specific carbonic acid can be carried out in the presence of a suitable catalyst, preferably in a suitable organic solvent.

As a catalyst used here, an organic base can be used and a well-known compound can be used as what is called a hardening accelerator which promotes reaction of an epoxy compound and a carboxylic acid. As this catalyst, it is preferable to use quaternary organic amine, and especially tetramethylammonium hydroxide etc. can be illustrated preferably.

The catalyst is preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyorganosiloxane having an epoxy group.

As an organic solvent used at the time of reaction of the polyorganosiloxane which has an epoxy group with specific carbonic acid, a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, an amide compound, an alcohol compound, etc. are mentioned, for example. Of these, ether compounds, ester compounds, and ketone compounds are preferred in view of solubility of raw materials and products and ease of purification of products. The solvent is used in an amount such that the solid content concentration (the ratio of the total weight of the components other than the solvent in the reaction solution to the total weight of the solution) is preferably 0.1% by weight or more, and more preferably 5 to 50% by weight. .

Reaction temperature becomes like this. Preferably it is 0-200 degreeC, More preferably, it is 50-150 degreeC.

The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

It is preferable to provide the preparation of a polymer composition after refine | purifying the polyorganosiloxane (A) obtained as mentioned above by any of the manufacturing methods 1-4 by a suitable well-known method.

[(C) Organic Solvent]

Examples of the organic solvent (C) in the present invention include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, and N, N-dimethyl. Acetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol Ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone , Isoamyl propionate, isoamyl isobutylate, diisopentyl ether and the like.

[Other Ingredients]

In addition to the above polymers (A), polymers (B), and (C) organic solvents, the polymerizable composition in the present invention may contain other components as necessary, so long as the effects of the present invention are not attenuated. . Examples of such other components include a polymerizable unsaturated compound, a photopolymerization initiator, a radical scavenger, a compound having at least one epoxy group in the molecule (hereinafter referred to as an "epoxy compound"), a functional silane compound, a surfactant, and the like. These, and 1 or more types chosen from these can be used.

{Polymerizable Unsaturated Compound}

Examples of the polymerizable unsaturated compound optionally used in the present invention include di (meth) acrylate having a biphenyl structure, di (meth) acrylate having a phenyl-cyclohexyl structure, and 2,2-diphenylpropane. Di (meth) acrylate having a structure, di (meth) acrylate having a diphenylmethane structure, di-thio (meth) acrylate having a diphenylthioether structure and other compounds (B-1), methacryl Acid-5ξ-cholestan-3-yl, methacrylic acid 4- (4'-phenyl-bicyclohexyl-4-yl) phenyl ester, methacrylic acid 4-octyloxyphenyl ester, methacrylic acid 4- (4 -Pentyl cyclohexyl) phenyl ester, etc. are mentioned.

As a usage ratio of such a polymerizable unsaturated compound, it is preferable to set it as 100 weight part or less with respect to a total of 100 weight part of a polymer (A) and a polymer (B), and to make it 5 to 50 weight part or less more. desirable.

{Photopolymerization initiator}

As said photoinitiator, (alpha)-diketone, an acyloin, an acyloin ether, a benzophenone compound, an acetophenone compound, a quinone compound, a halogen compound, an acylphosphine oxide, an organic peroxide etc. are mentioned, for example. .

As a photoinitiator, it is preferable to use a benzophenone compound from a viewpoint of high thermal stability, Especially, a thioxanthone, 2, 4- diethyl thioxanthone, a thioxanthone-4- sulfonic acid, benzophenone, 4 1 type selected from the group consisting of 4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, and phenyl- (4-p-tolylsulfanyl-phenyl) -methanone It is preferable to use the above.

It is preferable that the use ratio of the photoinitiator in the polymer composition in this invention shall be 30 weight part or less with respect to a total of 100 weight part of a polymer (A) and a polymerizable unsaturated compound, and is 0.5-30 weight part It is more preferable, and it is especially preferable to use 1-20 weight part.

{Radical scavenger}

The radical scavenger is a reaction in which the polymerizable carbon-carbon double bond possessed by the polymer (A) is not preferred by heating, which is preferably performed when the polymer composition according to the present invention is applied onto a substrate to form a coating film. In order to avoid causing this, it may be contained in the polymer composition in the present invention.

As a specific example of such a radical trapping agent, for example, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3, 5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N'-hexane-1,6-diylbis [3- (3,5 -Di-tert-butyl-4-hydroxyphenylpropionamide), 3,3 ', 3 ", 5'5" -hexa-tert-butyl-α, α', α "-(mesitylene-2,4 , 6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-tria True-2,4,6 (1H, 3H, 5H) -trione, etc. can be mentioned, One or more types selected from these can be used.

The use ratio of the radical trapping agent in this invention becomes like this. Preferably it is 10 weight part or less with respect to a total of 100 weight part of a polymer (A) and a polymerizable unsaturated compound, More preferably, it is 0.1-5 weight It is wealth.

{Epoxy compound}

Although the said epoxy compound is a compound which has at least 1 epoxy group in a molecule | numerator, the case where said polymer (A) has an epoxy group is excluded.

As an epoxy compound in this invention, the compound which has N, N- diglycidylamino group is preferable, As a specific example, N, N, N ', N'- tetraglycidyl-m-xyl Rendiamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N , N- diglycidyl-benzylamine, N, N- diglycidyl-aminomethylcyclohexane, N, N- diglycidyl-cyclohexylamine, etc. are mentioned, 1 type chosen from these The above can be used.

The compounding ratio of these epoxy compounds becomes like this. Preferably it is 40 weight part or less with respect to 100 weight part of polymers (A), More preferably, it is 30 weight part or less.

{Functional silane compound}

As said functional silane compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidepropyltrimethoxysilane, 3-ureidepropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimeth And methoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane and the like.

The compounding ratio of these functional silane compounds becomes like this. Preferably it is 2 weight part or less with respect to 100 weight part of polymers (A), More preferably, it is 0.2 weight part or less.

{Surfactants}

As said surfactant, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a silicone surfactant, a polyalkylene oxide surfactant, a fluorine-containing surfactant etc. are mentioned, for example.

When the polymer composition in the present invention contains a surfactant, the content ratio is preferably 10 parts by weight or less, more preferably 1 part by weight or less based on 100 parts by weight of the polymer composition.

[Polymer Composition]

The polymer composition used in the present invention is a polymer (A) or a mixture of a polymer (A) and a polymer (B), or any other component optionally used in these and the like (C) organic It is preferable to prepare as a solution which melt | dissolved in the solvent.

As a usage ratio of the polymer (B) in a polymer composition, it is preferable to set it as 95 weight% or less with respect to the sum total of a polymer (A) and a polymer (B), It is preferable to set it as 50 to 95 weight%, Furthermore, 60 It is preferable to set it as -90 weight%.

As a usage ratio of (C) an organic solvent, it is a ratio which solid content concentration (the ratio which the total weight of components other than the (C) organic solvent in a polymer composition occupies for the total weight of a polymer composition) of 1-15 weight% of a polymer composition. It is preferable to, and it is more preferable to set it as the ratio used as 1.5 to 8 weight%.

<Method of Manufacturing Liquid Crystal Display Element>

The manufacturing method of the liquid crystal display element of this invention,

On the said conductive film of a pair of board | substrates which have a conductive film, the above-mentioned polymer composition is apply | coated, respectively, and a coating film is formed,

A pair of substrates on which the coating film is formed are disposed to face each other such that the coating film is opposed to each other via a layer of liquid crystal molecules to form a liquid crystal cell,

And a step of irradiating light to the liquid crystal cell in a state where a voltage is applied between the conductive films of the pair of substrates.

Here, as a board | substrate, For example, glass, such as float glass and a soda glass; A transparent substrate made of polyethylene such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, or the like can be used.

As the conductive film, a transparent conductive film is preferably used. For example, an NESA (registered trademark) film made of SnO ₂ , an ITO film made of In ₂ O ₃ -SnO ₂ , and the like can be used. It is preferable that this conductive film is a patterned conductive film partitioned into a plurality of regions, respectively. With such a conductive film configuration, the direction of the pretilt angle of the liquid crystal molecules can be changed for each region by applying a different voltage for each region when a voltage is applied between the conductive films (to be described later). It becomes possible to widen.

In order to apply | coat a polymer composition on the said electrically conductive film of such a board | substrate, it can be based on suitable coating methods, such as a roll coater method, a spinner method, the printing method, the inkjet method, for example. After application | coating, the said coating surface is preheated (prebaked) and then baked (postbaking), and a coating film is formed. The prebaking conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C, and the postbaking conditions are preferably 120 to 300 ° C, more preferably 150 to 250 ° C, preferably 5 to 200 minutes, more preferably Is 10 to 100 minutes. The film thickness of the coating film after postbaking becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

The coating film formed in this way may be used as it is for the manufacture of the liquid crystal cell of a next process as it is, or you may perform a rubbing process with respect to a coating film surface as needed before manufacture of a liquid crystal cell. This rubbing process can be performed by rubbing in a fixed direction with the roll which wound the cloth which consists of fibers, such as nylon, a rayon, and cotton, with respect to a coating film surface, for example. Here, as described in Patent Document 2 (Japanese Patent Laid-Open Publication No. Hei 5-107544), after a rubbing treatment is performed, a resist film is formed on a part of the coating film surface, and further in a direction different from the previous rubbing treatment. After performing a rubbing process, the process of removing a resist film is performed, and it is possible to further improve the field of view characteristic of the liquid crystal display element obtained by making it into the rubbing direction different for every area | region.

Subsequently, a pair of substrates on which the coating film is formed are disposed to face each other so that the coating film faces through a layer of liquid crystal molecules to form a liquid crystal cell.

As a liquid crystal molecule used here, the nematic liquid crystal which has negative dielectric anisotropy is preferable, For example, dicyano benzene type liquid crystal, a pyridazine type liquid crystal, a siphon base type liquid crystal, a cyan clock liquid crystal, a biphenyl type A liquid crystal, a phenyl cyclohexane type liquid crystal, etc. can be used. It is preferable that the thickness of the layer of liquid crystal molecules shall be 1-5 micrometers.

For producing a liquid crystal cell using such a liquid crystal, the following two methods are mentioned, for example.

As a 1st method, two board | substrates are opposingly arranged through a gap (cell gap) so that each liquid crystal aligning film may oppose, and the peripheral part of two board | substrates is joined using a sealing agent, and the board | substrate surface And after filling and filling the liquid crystal into the cell gap partitioned by the sealing agent, the liquid crystal cell can be produced by sealing the injection hole. Or as a 2nd method, after apply | coating an ultraviolet-ray curable sealing compound, for example to the predetermined position on one of the two board | substrates with which the liquid crystal aligning film was formed, and further dropping a liquid crystal on the liquid crystal aligning film surface, A liquid crystal cell can be manufactured by bonding another board | substrate so that a liquid crystal aligning film may oppose, spreading a liquid crystal on the whole surface of a board | substrate, then irradiating ultraviolet light to the whole surface of a board | substrate, and hardening a sealing compound.

Thereafter, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates.

The voltage applied here can be, for example, 5 to 50 V DC or alternating current.

As the light to be irradiated, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. As a light source of irradiation light, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc. can be used, for example. Ultraviolet rays in the above preferred wavelength region can be obtained by means of using the light source together with a filter, a diffraction grating, or the like, for example. As an irradiation amount of light, Preferably it is 1,000 J / m <2> or less than 100,000 J / m <2>, More preferably, it is 1,000-50,000 J / m <2>. In the manufacture of the liquid crystal display element of the conventionally known PSA mode, although it was necessary to irradiate about 100,000 J / m <2> light, in the method of this invention, the light irradiation amount is 50,000 J / m <2> or less, Furthermore, 10,000 J / m <2> or less Even if it is set as desired, a desired liquid crystal display element can be obtained, and it can contribute to the reduction of the manufacturing cost of a liquid crystal display element, and can lower the electrical characteristic resulting from strong light irradiation, and the fall of long-term reliability.

And a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell after performing the above process. As a polarizing plate used here, the polarizing plate etc. which sandwiched the polarizing film called "H film | membrane" which absorbed iodine while extending | stretching polyvinyl alcohol by the cellulose acetate protective film, or the polarizing plate which consists of H film itself are mentioned.

Example

Synthesis of Polymer (A)

Synthesis Example A-1

In a flask equipped with a cooling tube and a stirrer, 64 g of p-vinylbenzyl glycidyl ether, 20 g of N-phenylmaleimide and 16 g of 4- (4'-n-pentylbicyclohexyl-4-yl) phenyl methacrylate were added. It melt | dissolved in 300 g of diethylene glycol diethyl ethers, Furthermore, 8 g of 2,2'- azobisisobutyronitrile and 8 g of (alpha)-methylstyrene dimers were added and nitrogen-substituted. Thereafter, the temperature of the reaction system was increased to 80 DEG C while stirring was continued with nitrogen bubbling, and the polymerization was carried out for 5 hours while preserving this temperature.

Subsequently, 28 g of methacrylic acid, 0.5 g of p-methoxyphenol and 4.4 g of tetrabutylammonium bromide were added to the reaction solution, and the reaction was carried out at a temperature of 120 ° C. for 9 hours. Further, 12.5 g of succinic anhydride was added and the reaction was carried out at a temperature of 100 ° C. for 6 hours, followed by washing with water twice while maintaining the temperature of the reaction mixture at 85 ° C., and concentrated under reduced pressure to obtain a concentrated product. Ethylene glycol diethyl ether was added and diluted to obtain a solution (polymer concentration of 32.2% by weight) containing the polymer (A-1). GPC was measured about the obtained polymer (A-1), and Mw was 7,800 and Mn was 5,200.

Synthesis Example A-2

Into a flask equipped with a cooling tube and a stirrer, 3 g of 2,2'-azobisisobutyronitrile and 200 g of diethylene glycol diethyl ether were added, followed by 60 g of 2-hydroxyethyl (meth) acrylate and N-phenyl. 10 g of maleimide, 20 g of cholestanyl methacrylate, 10 g of styrene, and 5 g of α-methylstyrene dimer (chain transfer agent) were added to replace the nitrogen, followed by gentle stirring, and the temperature of the reaction system was raised to 80 ° C. It preserve | saved and superposed | polymerized for 5 hours.

Subsequently, 65 g of 2- (meth) acryloyloxyethyl isocyanate was added to the reaction solution, and the reaction was carried out at a temperature of 120 ° C. for 8 hours, followed by water washing twice while maintaining the temperature of the reaction system at 85 ° C., The mixture was concentrated at a reduced pressure, and diethylene glycol diethyl ether was added to the obtained concentrate to dilute to obtain a solution containing a polymer (A-2) (polymer concentration of 33.8 wt%). GPC was measured about the obtained polymer (A-2), and Mw was 8,900 and Mn was 5,800.

Comparative Synthesis Example

Synthesis Example a-1

To a flask equipped with a cooling tube and a stirrer, 3 g of 2,2'-azobisisobutyronitrile and 200 g of diethylene glycol diethyl ether were added, followed by 15 g of methacrylic acid, 30 g of N-phenylmaleimide, and cholestanyl. After adding 35 g of methacrylate, 20 g of styrene, and 5 g of α-methylstyrene dimer (chain transfer agent) to replace the nitrogen, the reaction system was heated to 80 ° C. while gently stirring was continued, and the temperature was kept at this temperature to polymerize for 3 hours. did. Thereafter, the reaction system was heated to 100 ° C, 0.5 g of 2,2'-azobisisobutyronitrile was added, and the polymerization was continued for 1 hour to further include a solution containing polymer (a-1) (polymer concentration 32.8 % By weight) was obtained. GPC was measured about the obtained polymer (a-1), and Mw was 11,700 and Mn was 6,100.

Synthesis of Polymer (B)

[Synthesis of Polyamic Acid]

Synthesis Example B-1

1,2,3,4-cyclobutanetetracarboxylic dianhydride 98 g (0.50 mol) as tetracarboxylic dianhydride and 110 g (0.50 mol) pyromellitic dianhydride and 4,4'-diaminodiphenylmethane as diamine 200 g (1.0 mole) was dissolved in a mixed solvent consisting of 230 g of N-methyl-2-pyrrolidone (NMP) and 2,100 g of gamma -butyrolactone, and reacted at 40 ° C for 3 hours, followed by gamma -butyrolactone By adding 1,350 g, a solution containing a polyamic acid (B-1) (polymer concentration of 10% by weight, solution viscosity of 125 mPa · s) was obtained.

Synthesis Example B-2

200 g (1.0 mole) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 210 g (1.0 mole) of 2,2'-dimethyl-4,4'-diaminobiphenyl as diamine Solution was dissolved in a mixed solvent consisting of 370 g of NMP and 3,300 g of γ-butyrolactone, and reacted at 40 ° C. for 3 hours to give a solution containing polyamic acid (B-2) (polymer concentration of 10% by weight and solution viscosity of 160 mPa). S) was obtained.

[Synthesis of imidized polymer]

Synthesis Example B-3

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 43 g (0.40 mol) of p-phenylenediamine and 3- (3,5-diaminobenzoyloxy) as diamine 52 g (0.10 mol) of cholestan were dissolved in 830 g of NMP, and the mixture was reacted at 60 ° C for 6 hours to obtain a polyamic acid solution. A small amount of the obtained polyamic acid solution was aliquoted, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight by adding NMP was 60 mPa · s.

Subsequently, 1,900 g of NMP was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system is replaced with a new NMP (pyridine and acetic anhydride used in the dehydration ring-closure reaction in this operation are removed to the outside of the system) to thereby remove the imidized polymer (B-3) having an imidation ratio of about 50%. A solution containing about 15% by weight was obtained. A small amount of the obtained imidized polymer was aliquoted, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight by adding NMP was 47 mPa · s.

[Synthesis of Polyorganosiloxane]

Synthesis Example B-4

45.2 g of propylene glycol monomethyl ether, 18.8 g of tetraethoxysilane, and 3.3 g of dodecyl triethoxysilane were added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube, and the mixture was stirred to obtain a silane compound. The mixed solution was prepared. Subsequently, after heating this solution to 60 degreeC, the oxalic acid solution which consists of 8.8 g of water and 0.1 g of oxalic acid was dripped here. After completion of the dropwise addition, the solution was heated at 90 ° C for 3 hours, and then cooled to room temperature. Next, the solution containing polyorganosiloxane (B-4) was prepared by adding 76.2 g of butyl cellosolves here.

The weight average molecular weight Mw of the polyorganosiloxane (B-4) contained in this solution was 11,000.

Example 1

<Preparation of a polymer composition>

A solution containing the polymer (A-1) obtained in Synthesis Example A-1 as the polymer (A) and a solution containing the polyamic acid (B-1) obtained in Synthesis Example B-1 as the polymer (B) And mixing so that the weight ratio of the polymer contained in each solution is (A-1) :( B-1) = 20: 80, and further (C) N-methyl-2-pyrrolidone (NMP) as an organic solvent. And butyl cellosolve (BC) was added and diluted, and it was set as the solution which BC concentration is 20 weight% with respect to all the organic solvent, and solid content concentration is 6.0 weight%.

The polymer composition was prepared by filtering this solution using the filter of 1 micrometer of pore diameters. The organic solvent composition of this polymer composition was diethylene glycol diethyl ether: NMP: gamma-butyrolactone: BC = 3: 20: 57: 20 (weight ratio).

<Production of Liquid Crystal Cells>

Using the polymer composition prepared above, the pattern (three types) and ultraviolet irradiation amount (three levels) of the transparent electrode were changed, the nine liquid crystal display elements were manufactured, and the following evaluation was carried out.

[Production of Liquid Crystal Cell Having Patternless Transparent Electrode]

The polymer composition prepared above was apply | coated on the transparent electrode surface of the glass substrate which has a transparent electrode which consists of an ITO film | membrane using a liquid crystal aligning film printing machine (made by Nippon Shashin-Insatsu Co., Ltd.), and for 1 minute on an 80 degreeC hotplate After heating (prebaking) to remove the solvent, it was heated (postbaking) for 10 minutes on a 150 ° C hot plate to form a coating film having an average film thickness of 600 kPa.

About this coating film, the rubbing process was performed by the rubbing machine which has the roll which rolled up the rayon cloth at roll rotation speed 400rpm, stage movement speed 3cm / sec, and hairpin indentation length 0.1mm. Thereafter, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then dried in a 100 ° C clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated and the pair (2 sheets) of the board | substrate which has a liquid crystal aligning film was obtained.

Moreover, the said rubbing process is a weak rubbing process performed in order to control the fall of a liquid crystal, and to perform orientation division by a simple method.

Next, after apply | coating the aluminum oxide sphere containing epoxy resin adhesive of diameter 5.5micrometer to the outer edge of the surface which has a liquid crystal aligning film, about one sheet of the said pair of board | substrates, a pair of board | substrate was It pressed so that a liquid crystal aligning film surface could face, and hardened the adhesive agent. Subsequently, after filling a nematic liquid crystal (MLC-6608 by Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal injection port, the liquid crystal cell was manufactured by sealing a liquid crystal injection port with an acryl-type photocuring adhesive.

The above operation was repeated to produce three liquid crystal cells having a transparent electrode without a pattern. One of them was used for evaluation of the pretilt angle mentioned later as it is. Each of the remaining two liquid crystal cells was subjected to light irradiation in the state where a voltage was applied between the conductive films by the following method, and then used for evaluation of the pretilt angle and the voltage holding ratio.

For two of the liquid crystal cells obtained above, an alternating current of 10 Hz at a frequency of 60 Hz is applied between the electrodes, and the ultraviolet light is 10,000 J / m 2 using an ultraviolet irradiation device using a metal halide lamp as the light source while the liquid crystal is being driven. Or it investigated with the irradiation amount of 100,000 J / m <2>. In addition, this irradiation amount is the value measured using the photometer measured by wavelength 365nm reference.

[Evaluation of Pretilt Angle]

For each liquid crystal cell prepared above, Non-Patent Document 2 (TJ Scheffer et al., J. Appl. Phys. Vol. 48, p. 1783 (1977)) and Non-Patent Document 3 (F. Nakano, et al., JPN) According to the method described in J. Appl. Phys. Vol. 19, p. 2013 (1980)), the value of the inclination angle from the substrate surface of the liquid crystal molecules measured by the crystal rotation method using the He-Ne laser beam is free. Tilt angle was used.

Table 1 shows each of the pretilt angles of the non-irradiated liquid crystal cell, the liquid crystal cell having an irradiation amount of 10,000 J / m 2, and the liquid crystal cell having an irradiation amount of 100,000 J / m 2.

[Evaluation of Voltage Integrity]

About each liquid crystal cell produced above, after applying the voltage of 5V at 23 degreeC in 60 microseconds application time and the span of 167 milliseconds, the voltage preservation rate after 167 milliseconds after application | release cancellation was measured. As a measurement apparatus, VHR-1 manufactured by Toyo Technica Co., Ltd. was used.

Table 1 shows the voltage holding ratios of the liquid crystal cell having an irradiation amount of 10,000 J / m 2 and the liquid crystal cell having an irradiation amount of 10,000 J / m 2.

[Production of Liquid Crystal Cell 1 with Patterned Transparent Electrode]

The polymer composition prepared above is patterned in the slit shape as shown in FIG. 1, and is a liquid crystal aligning film printing machine (Nippon-shasin company) on each electrode surface of the glass substrates A and B which respectively have the ITO electrode divided into the some area | region. After coating by Co., Ltd.), the solvent was removed by heating on a hot plate at 80 ° C. for 1 minute (prebaking), and then heated (post baking) on a hot plate at 150 ° C. for 10 minutes to obtain an average film thickness of 600 kPa. Formed a coating film. About this coating film, after performing ultrasonic cleaning in ultrapure water for 1 minute, it dried in a 100 degreeC clean oven for 10 minutes, and obtained the board | substrate which has a liquid crystal aligning film. This operation was repeated and the pair (2 sheets) of the board | substrate which has a liquid crystal aligning film was obtained.

Subsequently, after apply | coating the aluminum oxide sphere containing epoxy resin adhesive of diameter 5.5micrometer to the outer edge of the surface which has a liquid crystal aligning film with respect to one board | substrate of the said pair of board | substrates, so that a pair of board | substrates may face a liquid crystal aligning film surface. It crimp | bonded over and hardened the adhesive agent. Subsequently, after filling a nematic liquid crystal (MLC-6608 by Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal injection port, the liquid crystal cell was manufactured by sealing a liquid crystal injection port with an acryl-type photocuring adhesive.

The above operation was repeated to produce three liquid crystal cells having a patterned transparent electrode. One of them was used for evaluation of the response speed mentioned later as it is. For the remaining two liquid crystal cells, light is emitted at a dose of 10,000 J / m 2 or 100,000 J / m 2 in a state where a voltage is applied between the conductive films by the same method as in the production of the liquid crystal cell having the transparent electrode without the pattern. After the investigation, the response speed was evaluated.

In addition, the pattern of the electrode used here is a pattern similar to the electrode pattern in PSA mode.

[Evaluation of response speed]

About each liquid crystal cell manufactured above, the brightness of the light which permeate | transmitted the liquid crystal cell was irradiated by irradiating a visible light lamp first without applying a voltage, and this value was made into 0% of the relative transmittance. Next, the transmittance | permeability when AC 60V was applied for 5 second between the electrodes of a liquid crystal cell was measured similarly to the above, and this value was made into 100% of the relative transmittance | permeability.

At this time, when AC 60V was applied to each liquid crystal cell, the time until the relative transmittance shifted from 10% to 90% was measured, and this time was defined as the response speed and evaluated.

Table 1 shows the response speeds of the non-irradiated liquid crystal cell, the liquid crystal cell of irradiation amount 10,000 J / m 2, and the liquid crystal cell of irradiation amount 100,000 J / m 2, respectively.

[Production of Liquid Crystal Cell 2 with Patterned Transparent Electrodes]

A liquid crystal having the patterned transparent electrode, except that glass substrates A and B each having an ITO electrode patterned in a fishborn shape as shown in FIG. 2 were used using the polymer composition prepared above. In the same manner as in the manufacture of the cell 1, a non-irradiated liquid crystal cell, a liquid crystal cell having an irradiation amount of 10,000 J / m 2, and a liquid crystal cell having an irradiation amount of 100,000 J / m 2 were produced, and the evaluation was performed in the same manner as described above, respectively. Provided. The evaluation results are shown in Table 1.

Examples 2-4 and Comparative Examples 1 and 2

In the said Example 1, the polymer composition was prepared like Example 1 except having used the usage-amount of each component as Table 1, and various liquid crystal cells were produced and evaluated using this. In Comparative Example 2, two types of polymers (B) were used.

The evaluation results are shown in Table 1.

Example 5

A solution containing the polymer (A-2) obtained in Synthesis Example A-2 as polymer (A) and a polyorganosiloxane (B-4) obtained in Synthesis Example B-4 as polymer (B). The solution was mixed so that the weight ratio of the polymer contained in each solution was (A-2) :( B-4) = 40: 60, and also diethylene glycol diethyl ether (DEGDEE) and propylene glycol mono were used as an organic solvent. Methyl ether (PGMME) and butyl cellosolve (BC) were added and diluted, and it was set as the solution whose solvent concentration was DEGDEE: PGMME: BC = 5: 30: 65 (weight ratio), and solid content concentration was 6.0 weight%. The polymer composition was prepared by filtering this solution using the filter of 1 micrometer of pore diameters.

Various liquid crystal cells were produced and evaluated using the polymer composition prepared above.

The evaluation results are shown in Table 1.

In the method of this invention from the result of Table 1, when the ultraviolet irradiation amount is set to 100,000 J / m <2> (it is the value conventionally employ | adopted in PSA mode), the degree of the pretilt angle obtained will become excess, and 10,000 J / m <2> or less It turns out that it becomes an appropriate pretilt angle in the irradiation amount of. Moreover, even if the irradiation amount is small, a sufficiently fast response speed is obtained, and the voltage holding ratio is also excellent.

Therefore, according to the method of the present invention, the advantages of the PSA mode, or in addition to the new operation mode, can be realized with a small amount of light irradiation. A liquid crystal display device having a wide viewing angle, a fast response speed of liquid crystal molecules, a high transmittance and a high contrast can be manufactured without fear of lack.

1: ITO electrode
2: slit part
3: shading film

Claims (8)

On the said conductive film of a pair of board | substrates which have a conductive film, respectively
(A) the following formula (AI):

(In formula (AI), R is a hydrogen atom or a methyl group, and Y ¹ and Y ² are each independently an oxygen atom or a sulfur atom.)
A polymer having a group represented by
(C) organic solvent
A coating film is formed by applying a polymer composition containing
A pair of substrates on which the coating film is formed are disposed to face each other such that the coating film is opposed to each other via a layer of liquid crystal molecules to form a liquid crystal cell,
And a step of irradiating the liquid crystal cell with light while a voltage is applied between the conductive films of the pair of substrates. The method of claim 1,
The manufacturing method of the liquid crystal display element whose said (A) polymer is a (meth) acrylic-type polymer. The method of claim 2,
The polymer composition is further
(B) The manufacturing method of the liquid crystal display element which contains at least 1 sort (s) of polymer chosen from the group which consists of polyamic acid, its imidation polymer, and polyorganosiloxane. The method of claim 3,
The (B) polymer,
The manufacturing method of the liquid crystal display element which is at least 1 sort (s) of polymer chosen from the group which consists of polyamic acid which does not have group represented by said formula (AI), and its imidation polymer. The method according to any one of claims 1 to 4,
A method for producing a liquid crystal display element, wherein each of the conductive films is a patterned conductive film partitioned into a plurality of regions. (A) (meth) acrylic-type polymer which has group represented by said formula (AI) of Claim 1, and
(B) A polymer composition characterized by containing at least one polymer selected from the group consisting of polyamic acid, its imidized polymer and polyorganosiloxane. The method of claim 6,
Coating films are formed on the conductive films of the pair of substrates having the conductive films, respectively.
A pair of substrates on which the coating film is formed are disposed to face each other such that the coating film is opposed to each other via a layer of liquid crystal molecules to form a liquid crystal cell,
In the manufacturing method of the liquid crystal display element which goes through the process of irradiating light to the said liquid crystal cell in the state which applied the voltage between the conductive films which the said pair of board | substrates have,
A polymer composition, characterized in that it is used to form the coating film. It was manufactured by the manufacturing method of the liquid crystal display element in any one of Claims 1-4, The liquid crystal display element characterized by the above-mentioned.

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