TWI535773B - Resin composition, liquid crystal alignment material and retardation material - Google Patents

Resin composition, liquid crystal alignment material and retardation material Download PDF

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TWI535773B
TWI535773B TW100127999A TW100127999A TWI535773B TW I535773 B TWI535773 B TW I535773B TW 100127999 A TW100127999 A TW 100127999A TW 100127999 A TW100127999 A TW 100127999A TW I535773 B TWI535773 B TW I535773B
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resin composition
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film
liquid crystal
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安達勳
畑中真
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日產化學工業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation

Description

樹脂組成物、液晶配向材料及相位差材料Resin composition, liquid crystal alignment material, and phase difference material

本發明為有關樹脂組成物、液晶配向材料及相位差材料之發明。The present invention relates to a resin composition, a liquid crystal alignment material, and a phase difference material.

目前為止，以補償液晶顯示器之視角為目的時，多以於液晶晶元之外部配置相位差薄膜之方式進行。此情形中，相位差薄膜之種類則因液晶顯示器中液晶之顯示模式而有所差異。For the purpose of compensating the viewing angle of the liquid crystal display, the retardation film is often disposed outside the liquid crystal cell. In this case, the type of the retardation film differs depending on the display mode of the liquid crystal in the liquid crystal display.

例如，VA模式液晶顯示器之情形，為單獨使用薄膜之面內x及y方向以及厚度方向等3方向之折射率相異之二軸偏光板(plate)作為相位差薄膜，或，將單軸延伸所製作之正A偏光板與負C偏光板組合作為相位差薄膜之方式作為視角之補償。前者為使用二軸延伸所製作者，後者為單軸延伸所製作者。其中，使偏光板之薄膜面內x及y方向之折射率作為nx及ny，厚度方向之折射率作為nz之情形，正A偏光板為具有nx＞ny=nz之特性的相位差薄膜。又，負C偏光板為具有nx=ny＞nz之特性的相位差薄膜。For example, in the case of a VA mode liquid crystal display, a two-axis polarizing plate having a refractive index different in three directions such as in-plane x and y directions and a thickness direction of a film is used as a retardation film alone, or uniaxially stretched. The method of combining the positive A polarizing plate and the negative C polarizing plate produced as a retardation film is used as the compensation of the viewing angle. The former is produced by using a two-axis extension, and the latter is produced by a single-axis extension. In the case where the refractive index in the x and y directions of the film of the polarizing plate is nx and ny, and the refractive index in the thickness direction is nz, the positive A polarizing plate is a retardation film having a characteristic of nx>ny=nz. Further, the negative C polarizing plate is a retardation film having a characteristic of nx=ny>nz.

又，近年來，已就於液晶顯示器之液晶晶元內導入相位差材料以達到高反差化、低費用化或輕量化等目的而進行各種研究。隨後，則有形成該些相位差材料而使用聚合性液晶溶液之提案。具體而言，為將聚合性液晶溶液塗佈於液晶晶元內之適當部位，進行所期待之配向後，再經光硬化而形成相位差材料。In recent years, various studies have been conducted for the purpose of introducing a phase difference material into a liquid crystal cell of a liquid crystal display to achieve high contrast, low cost, or light weight. Subsequently, there is a proposal to form a phase difference material and use a polymerizable liquid crystal solution. Specifically, a polymerizable liquid crystal solution is applied to an appropriate portion of the liquid crystal cell, and after the desired alignment is performed, the phase difference material is formed by photocuring.

正A偏光板之情形中，為使用顯示水平配向性之聚合性液晶。又，負C偏光板之情形中，為使用顯示膽固醇(Cholesteric)配向或盤形(Discotic)配向性之聚合性液晶。此外，二軸偏光板之情形中，為顯示二軸配向性之聚合性液晶。因此，將具有二軸相位差之相位差材料導入液晶晶元內時，必須將顯示二軸配向性之聚合性液晶，或，顯示膽固醇配向性之聚合性液晶與顯示水平配向性之聚合性液晶層合使用。In the case of a positive A polarizing plate, a polymerizable liquid crystal exhibiting horizontal alignment is used. Further, in the case of a negative C polarizing plate, a polymerizable liquid crystal exhibiting a Cholesteric alignment or a discotic alignment property is used. Further, in the case of the biaxial polarizing plate, it is a polymerizable liquid crystal which exhibits biaxial alignment. Therefore, when introducing a phase difference material having a two-axis phase difference into a liquid crystal cell, it is necessary to display a polymerizable liquid crystal having biaxial alignment properties, or a polymerizable liquid crystal exhibiting cholesterol alignment property and a polymerizable liquid crystal exhibiting horizontal alignment. Laminated for use.

但是，顯示二軸配向性之聚合性液晶，已知其不容易形成厚膜化，目前尚未發現可顯示出必要之相位差特性的材料。又，層合顯示膽固醇配向性之聚合性液晶與顯示水平配向性之聚合性液晶之情形，將會造成製造步驟複雜化，而會有增大製造費用或降低產率等問題。However, it has been known that a polymerizable liquid crystal having a biaxial alignment property is not easily formed into a thick film, and a material which exhibits a necessary phase difference characteristic has not been found. Further, in the case of laminating a polymerizable liquid crystal exhibiting cholesterol alignment and a polymerizable liquid crystal exhibiting horizontal alignment, the manufacturing steps are complicated, and there are problems such as an increase in manufacturing cost or a decrease in productivity.

圖2為，使用以往技術形成液晶配向膜之液晶晶元的模式構成圖。該圖中，液晶層208為被挾夾於2片之基板201、211之間。於基板211上，形成ITO 210與配向膜209。又，基板201上，依序形成濾光膜202，與濾光膜(CF)之保護膜(Overcoat)(以下亦稱為CF保護膜)203，與配向膜204，與相位差材料205，與ITO 206，與配向膜207。Fig. 2 is a schematic view showing a configuration of a liquid crystal cell in which a liquid crystal alignment film is formed by a conventional technique. In the figure, the liquid crystal layer 208 is sandwiched between two substrates 201 and 211. On the substrate 211, an ITO 210 and an alignment film 209 are formed. Further, on the substrate 201, a filter film 202, an overcoat (hereinafter also referred to as a CF protective film) 203 of a filter film (CF), an alignment film 204, and a phase difference material 205 are formed. ITO 206, and alignment film 207.

以往之液晶晶元中，為形成上述相位差材料而必須於聚合性液晶硬化前形成配向，故其下層需具有可使液晶進行配向之膜，即，必須另外設置配向膜。配向膜為經由摩擦處理或偏光照射等步驟而形成。即，如圖2所示般，以往為於CF保護膜203上，形成配向膜204之膜後，於其上再形成由液晶單體等聚合性液晶所得之相位差材料205為一般之常用方法。即，形成濾光膜202之後，必須再層合CF保護膜203與配向膜204之2個層之方式予以形成，而造成製造步驟複雜化。In the conventional liquid crystal cell, in order to form the phase difference material, it is necessary to form an alignment before the polymerizable liquid crystal is cured. Therefore, the lower layer needs to have a film which can align the liquid crystal, that is, an alignment film must be separately provided. The alignment film is formed by a step such as rubbing treatment or polarized light irradiation. In other words, as shown in FIG. 2, a film of the alignment film 204 is formed on the CF protective film 203, and a phase difference material 205 obtained by forming a polymerizable liquid crystal such as a liquid crystal monomer is generally used as a general method. . That is, after the filter film 202 is formed, it is necessary to form two layers of the CF protective film 203 and the alignment film 204, which complicates the manufacturing process.

基於上述需求，目前極需要提供一種可以同時滿足不同需求特性之膜，及形成其之材料。具體而言，例如尋求可兼顧配向膜與CF保護膜之膜，與形成該膜之材料。如此，液晶顯示器於製造上，可享受到低費用化、消減製程數、提高產率等龐大的優點。Based on the above requirements, it is highly desirable to provide a film that can simultaneously satisfy different demand characteristics, and a material that forms the same. Specifically, for example, a film which can balance both the alignment film and the CF protective film and a material which forms the film are sought. In this way, the liquid crystal display can enjoy the advantages of low cost, reduced number of processes, and improved productivity.

又，對於兼具配向膜與CF保護膜之膜，則要求其可縮短配向處理所需之時間。但，於配向膜之製造步驟中，則必須使用於光配向技術。因此，兼具配向膜與CF保護膜之膜，則強力需求其可使用光配向性之材料作為構成內容。Further, in the case of a film having both the alignment film and the CF protective film, it is required to shorten the time required for the alignment treatment. However, in the manufacturing step of the alignment film, it is necessary to use it in the photoalignment technique. Therefore, in the case of a film having both an alignment film and a CF protective film, a material which can use photoalignment is strongly required as a constituent content.

此外，兼具配向膜與CF保護膜之膜中，亦要求具有更大之雙折射率。增大雙折射率時，則可賦予負C偏光板之特性。又，具備高雙折射特性時，可使層合於其上之二軸配向性聚合性液晶之膜厚度薄化，此外，僅塗佈水平配向性聚合性液晶時，亦可得到二軸特性。Further, in the film having both the alignment film and the CF protective film, a larger birefringence is also required. When the birefringence is increased, the characteristics of the negative C polarizer can be imparted. Further, when the high birefringence property is provided, the film thickness of the biaxially oriented polymerizable liquid crystal laminated thereon can be made thinner, and when only the horizontally oriented polymerizable liquid crystal is applied, the biaxial characteristics can be obtained.

一般而言，CF保護膜中，為使用具有高透明性之丙烯酸樹脂。隨後，經由熱或光使丙烯酸樹脂硬化時，可產生耐熱性或耐溶劑性(例如，專利文獻1或2)。In general, in the CF protective film, an acrylic resin having high transparency is used. Subsequently, when the acrylic resin is cured by heat or light, heat resistance or solvent resistance can be produced (for example, Patent Document 1 or 2).

但是，經由本發明者們之研究得知，以往之由熱硬化性或光硬化性之丙烯酸樹脂所構成之CF保護膜雖可得到透明性或耐溶劑性之物，但其即使照射偏光UV時，也無法得到充分之液晶配向性。因此確認以往之CF保護膜於未加工下，則無法適用於上述兼具配向膜與CF保護膜之膜。However, it has been found by the inventors of the present invention that a CF protective film composed of a thermosetting or photocurable acrylic resin can obtain transparency or solvent resistance, but it is irradiated with polarized UV. Also, there is no way to obtain sufficient liquid crystal alignment. Therefore, it has been confirmed that the conventional CF protective film is not applied to the film having the alignment film and the CF protective film as described above.

又，已知有使用具有聯苯基骨架之四羧酸二酐與具有脂環結構之二胺所形成之聚醯胺酸，可得到高透明且具有高雙折射率之聚醯胺酸之報告(專利文獻3)。但是，該聚醯胺酸即使偏光照射時，也無法得到充分之液晶配向性。即，該些高折射率之聚醯胺酸於未加工下，則無法適用於上述兼具配向膜與CF保護膜之膜。Further, it is known that a polyamic acid formed by using a tetracarboxylic dianhydride having a biphenyl skeleton and a diamine having an alicyclic structure can provide a report of a highly transparent polyhistamine having a high birefringence. (Patent Document 3). However, even when the polyacrylic acid is irradiated with polarized light, sufficient liquid crystal alignment property cannot be obtained. That is, these high refractive index polyamic acids cannot be applied to the film having the alignment film and the CF protective film as described above.

又，亦有提出側鏈具有桂皮醯基或查耳酮基等光二聚化部位之丙烯酸樹脂，於照射偏光UV時，可得到充分之液晶配向性之報告(專利文獻4)。但是，依本發明者們之研究得知，即使使通常之顯示器用液晶進行配向，再照射充分之偏光UV曝光量(例如100mJ/cm2)時，仍無法充分賦予上述兼具配向膜與CF保護膜之膜的機能。具體而言，例如對前述丙烯酸樹脂照射偏光UV後，再於其上塗佈聚合性液晶溶液之情形，則會降低對丙烯酸樹脂溶液之耐性，而使下層之丙烯酸樹脂之膜溶解。因此，對於聚合性液晶而言，也無法得到充分之配向性。Further, an acrylic resin having a photodimerization site such as a cinnabar base or a chalcone group in the side chain has been proposed, and when the polarized UV is irradiated, a sufficient liquid crystal alignment property can be obtained (Patent Document 4). However, according to studies by the inventors of the present invention, even when a normal liquid crystal for a display is aligned and a sufficient amount of polarized UV exposure (for example, 100 mJ/cm 2 ) is applied, the alignment film and the CF are not sufficiently provided. The function of the membrane of the protective film. Specifically, for example, when the polarizing UV is applied to the acrylic resin and the polymerizable liquid crystal solution is applied thereon, the resistance to the acrylic resin solution is lowered, and the film of the lower acrylic resin is dissolved. Therefore, sufficient alignment properties cannot be obtained for the polymerizable liquid crystal.

又，經由1J/cm2以上之大量的偏光UV曝光量時，亦可提高上述丙烯酸樹脂中的光二聚化反應之反應率。因此，增大曝光量對於提高聚合性液晶之配向性仍有其可能性。但是，為進行各種配向處理之目的，而對以縮短時間為目的而進行光配向技術之研究時，得知伴隨曝光時間之長時間化，曝光量之增大仍有其一定之限度。Moreover, when a large amount of polarized UV exposure amount of 1 J/cm 2 or more is used, the reaction rate of the photodimerization reaction in the above acrylic resin can also be improved. Therefore, increasing the exposure amount has a possibility of improving the alignment of the polymerizable liquid crystal. However, in order to perform various alignment treatments, it has been found that when the optical alignment technique is performed for the purpose of shortening the time, it is known that the exposure amount is increased for a long period of time, and the increase in the exposure amount is still limited.

此外，依本發明者們之研究結果，得知即使提高反應率，僅進行以產生液晶配向性為目的之光二聚化反應時，仍未能充分進行交聯反應，而無法實現膜所應具有之充分之耐熱性。即，確認由上述丙烯酸樹脂所形成之膜，於提高反應率時，在以製造液晶晶元為目的所進行之加熱處理時，將會引起極大之膜收縮。Further, according to the findings of the present inventors, it has been found that even when the photodimerization reaction for the purpose of generating liquid crystal alignment is performed even if the reaction rate is increased, the crosslinking reaction is not sufficiently performed, and the film is not required to have a film. Fully heat resistant. In other words, when the film formed of the above acrylic resin is confirmed, when the reaction rate is increased, the film shrinkage is caused to a large extent in the heat treatment for the purpose of producing a liquid crystal cell.

[先前技術文獻][Previous Technical Literature] [專利文獻][Patent Literature]

[專利文獻1]　特開2000-103937號公報[Patent Document 1] JP-A-2000-103937

[專利文獻2]　特開2000-119472號公報[Patent Document 2] JP-A-2000-119472

[專利文獻3] WO2008010483A1號公報[Patent Document 3] WO2008010483A1

[專利文獻4]　特許4011652號[Patent Document 4] License No. 4011652

本發明即為基於以上見解與研究所提出之發明。即，本發明之目的為利用光配向技術，使熱硬化後形成高感度之聚合性液晶形成配向，又，提供一種具有高雙折射率、高耐溶劑性、耐熱性及高透明性之樹脂組成物。The present invention is an invention based on the above findings and research. That is, the object of the present invention is to form a high-sensitivity polymerizable liquid crystal to form an alignment by thermal alignment using a photo-alignment technique, and to provide a resin composition having high birefringence, high solvent resistance, heat resistance, and high transparency. Things.

本發明之其他目的及優點，可由以下述載而明確得知。Other objects and advantages of the present invention will be apparent from the following description.

本發明之第1之態樣為，一種樹脂組成物，其特徵為含有According to a first aspect of the present invention, there is provided a resin composition characterized by comprising

(A)具有由疏水性基所形成之光二聚化部位與由親水性基所形成之熱交聯部位之丙烯酸共聚物，與(A) an acrylic copolymer having a photodimerization site formed by a hydrophobic group and a thermal crosslinking site formed by a hydrophilic group, and

(B)具有芳香環部位之聚醯亞胺前驅物，與(B) a polyimide precursor having an aromatic ring moiety, and

(C)使(A)成分與(B)成分交聯之交聯劑。(C) A crosslinking agent which crosslinks the component (A) and the component (B).

本發明之第1之態樣中，(A)成分，以含有具有光二聚化部位之單體與具有熱交聯部位之單體的單體混合物經聚合反應所得之丙烯酸共聚物為佳。In the first aspect of the invention, the component (A) is preferably an acrylic copolymer obtained by polymerizing a monomer mixture containing a monomer having a photodimerization site and a monomer having a thermal crosslinking site.

本發明之第1之態樣中，(A)成分，相對於全單體混合物之合計量，以含有25莫耳%至90莫耳%之具有光二聚化部位之單體的單體混合物經聚合反應所得之丙烯酸共聚物為佳。In the first aspect of the present invention, the component (A) is a monomer mixture containing 25 to 20 mol% of a monomer having a photodimerization site, relative to the total amount of the all monomer mixture. The acrylic copolymer obtained by the polymerization reaction is preferred.

本發明之第1之態樣中，(A)成分之光二聚化部位以桂皮醯基為佳。In the first aspect of the present invention, the photodimerization site of the component (A) is preferably a cinnamyl group.

本發明之第1之態樣中，(A)成分之熱交聯部位以羥基或羧基為佳。In the first aspect of the present invention, the thermally crosslinked portion of the component (A) is preferably a hydroxyl group or a carboxyl group.

本發明之第1之態樣中，(B)成分之聚醯亞胺前驅物以主鏈具有聯苯基結構為佳。In the first aspect of the invention, the polyimine precursor of the component (B) preferably has a biphenyl structure in the main chain.

本發明之第1之態樣中，(B)成分，以含有四羧酸二酐與二胺化合物經共聚反應所得之結構單位之聚醯亞胺前驅物，且四羧酸二酐及二胺化合物之至少一者為具有聯苯基結構者為佳。In the first aspect of the invention, the component (B) is a polyimine precursor containing a structural unit obtained by copolymerization of a tetracarboxylic dianhydride and a diamine compound, and a tetracarboxylic dianhydride and a diamine. It is preferred that at least one of the compounds is a biphenyl structure.

本發明之第1之態樣中，四羧酸二酐以聯苯基四羧酸二酐為佳。In the first aspect of the present invention, the tetracarboxylic dianhydride is preferably biphenyltetracarboxylic dianhydride.

本發明之第1之態樣中，(B)成分以結構單位具有三氟甲基之聚醯亞胺前驅物為佳。In the first aspect of the invention, the component (B) is preferably a polyimine precursor having a trifluoromethyl group in a structural unit.

本發明之第1之態樣中，(B)成分之聚醯亞胺前驅物以主鏈具有脂環結構者為佳。In the first aspect of the present invention, the polyimine precursor of the component (B) preferably has an alicyclic structure in the main chain.

本發明之第1之態樣中，(B)成分以含有四羧酸二酐與二胺化合物經共聚反應所得之結構單位之聚醯亞胺前驅物，且四羧酸二酐及二胺化合物之至少一者為具有脂環結構者為佳。In the first aspect of the invention, the component (B) is a polyimine precursor containing a structural unit obtained by copolymerization of a tetracarboxylic dianhydride and a diamine compound, and a tetracarboxylic dianhydride and a diamine compound. At least one of them is preferably an alicyclic structure.

本發明之第1之態樣中，(C)成分之交聯劑以具有羥甲基或烷氧基羥甲基之交聯劑為佳。In the first aspect of the invention, the crosslinking agent of the component (C) is preferably a crosslinking agent having a methylol group or an alkoxymethylol group.

本發明之第1之態樣中，以(A)成分與(B)成分之合計量100質量份為基準，以含有10至100質量份之(C)成分為佳。In the first aspect of the present invention, it is preferred to contain 10 to 100 parts by mass of the component (C) based on 100 parts by mass of the total of the components (A) and (B).

本發明之第1之態樣中，以再含有(D)成分之酸或熱酸發生劑者為佳。In the first aspect of the present invention, it is preferred that the acid or the thermal acid generator further contains the component (D).

本發明之第1之態樣中，以(A)成分與(B)成分之合計量100質量份為基準，以含有0.1至10質量份之(D)成分為佳。In the first aspect of the invention, it is preferred to contain 0.1 to 10 parts by mass of the component (D) based on 100 parts by mass of the total of the components (A) and (B).

本發明之第2之態樣為，有關使用本發明之第1之態樣的樹脂組成物為特徵所得到之液晶配向材料。According to a second aspect of the present invention, there is provided a liquid crystal alignment material obtained by using the resin composition of the first aspect of the present invention.

本發明之第3之態樣為，有關使用本發明之第1之態樣之樹脂組成物所得之硬化膜為特徵所形成之相位差材料。According to a third aspect of the present invention, there is provided a phase difference material formed by using a cured film obtained by using the resin composition of the first aspect of the present invention.

[發明之效果][Effects of the Invention]

本發明之第1之態樣之樹脂組成物，可得到除具有高雙折射率、高透明性、高耐溶劑性及高耐熱性以外，亦可形成液晶之光配向的硬化膜。In the resin composition of the first aspect of the present invention, a cured film having a high refractive index, high transparency, high solvent resistance, and high heat resistance can be obtained, and light alignment of the liquid crystal can be formed.

依本發明之第2之態樣時，可得到具有高雙折射率，且為優良之光透過性、耐溶劑性及配向性的液晶配向材料。According to the second aspect of the present invention, a liquid crystal alignment material having high birefringence and excellent light transmittance, solvent resistance and alignment property can be obtained.

依本發明之第3之態樣時，可得到對液晶晶元內進行配置之相位差材料。使用該相位差材料之液晶晶元，可提高其反差比。According to the third aspect of the present invention, a phase difference material which is disposed in the liquid crystal cell can be obtained. The liquid crystal cell of the phase difference material can be used to increase the contrast ratio.

本發明為有關樹脂組成物，與使用該樹脂組成物所形成之液晶配向材料，與使用該樹脂組成物所得之硬化膜所形成之相位差材料之發明。更詳言之，為有關可形成具有高雙折射率，與高透明性，與液晶配向能，與高耐溶劑性，與耐熱性之硬化膜的樹脂組成物，與使用該樹脂組成物所形成之液晶配向材料，與使用該液晶配向材料所形成之相位差材料之發明。本發明之樹脂組成物，適合作為液晶顯示器中，具有作為CF保護膜之機能的膜，又，對以形成相位差層為目的聚合性液晶具有配向機能，故也適合用於形成內置相位差層。The present invention relates to a resin composition, a liquid crystal alignment material formed using the resin composition, and a phase difference material formed by using a cured film obtained by using the resin composition. More specifically, it relates to a resin composition which can form a cured film having high birefringence, high transparency, liquid crystal alignment energy, high solvent resistance, and heat resistance, and is formed by using the resin composition. The invention relates to a liquid crystal alignment material and a phase difference material formed by using the liquid crystal alignment material. The resin composition of the present invention is suitable as a film for a function as a CF protective film in a liquid crystal display, and has an alignment function for a polymerizable liquid crystal for forming a phase difference layer, and is therefore suitable for forming a built-in phase difference layer. .

以下，將列舉具體例示詳細說明本發明之樹脂組成物、液晶配向材料及相位差材料。Hereinafter, the resin composition, the liquid crystal alignment material, and the phase difference material of the present invention will be described in detail by way of specific examples.

本實施形態之樹脂組成物，為形成具有光配向性之熱硬化膜為目的之樹脂組成物，即為光配向性熱硬化膜形成用之樹脂組成物之意。又，具有光配向性之熱硬化膜係指，經由加熱而硬化，受到偏光曝光而引發液晶之配向性能的硬化膜之意。The resin composition of the present embodiment is intended to form a resin composition for forming a thermosetting film having photo-alignment properties, that is, a resin composition for forming a photo-alignment thermosetting film. Further, the thermosetting film having photo-alignment properties means a cured film which is cured by heating and which is subjected to polarized light exposure to cause alignment properties of liquid crystal.

本實施形態之樹脂組成物為含有，(A)成分之具有光二聚化部位及熱交聯部位之丙烯酸共聚物，與(B)成分之聚醯亞胺前驅物，與(C)成分之交聯劑。The resin composition of the present embodiment is an acrylic copolymer containing a photodimerization site and a thermal crosslinking site of the component (A), and a polybendimimine precursor of the component (B), and a component of the component (C). Joint agent.

更具體而言，(A)成分中，丙烯酸共聚物之光二聚化部位為由疏水性基所形成，丙烯酸共聚物之熱交聯部位為由親水性基所形成。又，(B)成分之聚醯亞胺前驅物為具有芳香環部位者。此外，(C)成分之交聯劑為，可使(A)成分與(B)成分交聯之成份。More specifically, in the component (A), the photodimerization site of the acrylic copolymer is formed of a hydrophobic group, and the thermal crosslinking site of the acrylic copolymer is formed of a hydrophilic group. Further, the polyimine precursor of the component (B) is a member having an aromatic ring moiety. Further, the crosslinking agent of the component (C) is a component which can crosslink the component (A) and the component (B).

即，本實施形態之樹脂組成物為含有，That is, the resin composition of the present embodiment contains,

(A)具有疏水性基所形成之光二聚化部位，與親水性基所形成之熱交聯部位之丙烯酸共聚物，與(A) an acrylic copolymer having a photodimerization site formed by a hydrophobic group and a thermal crosslinking site formed by a hydrophilic group, and

(B)具有芳香環部位之聚醯亞胺前驅物，與(B) a polyimide precursor having an aromatic ring moiety, and

(C)使(A)成分與(B)成分交聯之交聯劑所構成者。(C) A composition comprising a crosslinking agent which crosslinks the component (A) and the component (B).

此外，本實施形態之樹脂組成物，除(A)成分、(B)成分及(C)成分以外，可再含有(D)成分之酸或光酸發生劑，及/或，(E)成分之增感劑。Further, the resin composition of the present embodiment may further contain an acid or photoacid generator of the component (D) in addition to the components (A), (B) and (C), and/or (E) component. The sensitizer.

本實施形態之樹脂組成物中，含有(A)成分時，對於使用該樹脂組成物所得之硬化膜，經由光配向處理可賦予液晶配向性能。即，(A)成分之丙烯酸共聚物，於具有疏水性基所形成之光二聚化部位與親水性基所形成之熱交聯部位時，經由塗佈後之加熱，可於後述熱交聯部位進行熱交聯反應而硬化。此時，疏水性基所形成之光二聚化部位除存在於硬化膜之表面附近以外，亦以突出於表面之自由狀態下存在。以該狀態為基礎時，經由偏光UV曝光等而進行光二聚化反應時，可於硬化膜之表面附近產生優良之液晶配向性能。因此，硬化膜上塗佈聚合性液晶時，會造成高疏水性之聚合性液晶，與由丙烯酸共聚物之疏水性基所形成之光二聚化部位有效率地進行相互作用，而可實現高感度之液晶配向。In the resin composition of the present embodiment, when the component (A) is contained, the cured film obtained by using the resin composition can impart liquid crystal alignment performance via photo-alignment treatment. In other words, the acrylic copolymer of the component (A) can be thermally crosslinked as described later when it is heated at the time of heat transfer by a photodimerization site formed by a hydrophobic group and a hydrophilic group. It is hardened by a thermal crosslinking reaction. At this time, the photodimerization site formed by the hydrophobic group exists in addition to the vicinity of the surface of the cured film, and also exists in a free state protruding from the surface. When the photodimerization reaction is carried out by polarized UV exposure or the like based on this state, excellent liquid crystal alignment performance can be produced in the vicinity of the surface of the cured film. Therefore, when a polymerizable liquid crystal is applied onto the cured film, a highly hydrophobic polymerizable liquid crystal is formed, and the photodimerization site formed by the hydrophobic group of the acrylic copolymer is efficiently interacted to achieve high sensitivity. Liquid crystal alignment.

又，(A)成分具有熱交聯部位。該熱交聯部位可為由親水性基所形成者，如此，可與後述(C)成分之交聯劑之間，產生有效率的熱交聯反應。其結果，除光二聚化部位以外，亦可經由熱反應而導入交聯化部位，而增大交聯部位之數目。因此，經由於硬化膜上塗佈聚合性液晶溶液，即可防止硬化膜之溶解。又，於液晶晶元之製造步驟中的加熱環境下，亦可抑制硬化膜產生熱收縮現象。Further, the component (A) has a thermally crosslinked portion. The thermally crosslinked portion may be formed of a hydrophilic group, and thus an efficient thermal crosslinking reaction may be generated between the crosslinking agent of the component (C) described later. As a result, in addition to the photodimerization site, the crosslinked portion can be introduced via a thermal reaction to increase the number of crosslinked sites. Therefore, dissolution of the cured film can be prevented by applying a polymerizable liquid crystal solution to the cured film. Further, in the heating environment in the manufacturing process of the liquid crystal cell, the heat shrinkage phenomenon of the cured film can also be suppressed.

又，本實施形態之樹脂組成物，於含有(B)成分時，可調整使用該樹脂組成物所得之硬化膜的雙折射性。即，(B)成分之聚醯亞胺前驅物，經由熱反應而形成聚醯亞胺而構成硬化膜，該聚醯亞胺前驅物之主鏈上於選擇包含苯環結構或聯苯結構等之分子結構時，則可對硬化膜賦予高雙折射性。Further, in the resin composition of the present embodiment, when the component (B) is contained, the birefringence of the cured film obtained by using the resin composition can be adjusted. That is, the polyimine precursor of the component (B) forms a polyimine by thermal reaction to form a cured film, and the main chain of the polyimide precursor is selected to include a benzene ring structure or a biphenyl structure. In the case of the molecular structure, high-birefringence can be imparted to the cured film.

又，此時，仍會有硬化膜之光透過性，即透明性降低之疑慮，其經由選擇構成聚醯亞胺前驅物之化合物的分子結構時，則可抑制透過率之降低。例如，構成聚醯亞胺前驅物之化合物，於選擇具有脂環結構之化合物時，則可賦予硬化膜高透明性。即，經由適當設計聚醯亞胺前驅物之分子結構結果，則對硬化膜可同時賦予高雙折射性與高透明性等二者。Moreover, in this case, there is still a concern that the light transmittance of the cured film, that is, the transparency is lowered, and when the molecular structure of the compound constituting the polyimide precursor is selected, the decrease in the transmittance can be suppressed. For example, a compound constituting a polyimide precursor can impart high transparency to a cured film when a compound having an alicyclic structure is selected. That is, by appropriately designing the molecular structure of the polyimide precursor, the cured film can simultaneously impart both high birefringence and high transparency.

此外，本實施形態之樹脂組成物，因含有(C)成分，故對於使用該樹脂組成物所得之硬化膜，可經由熱反應而導入交聯部位。即，如上所述般，與(A)成分之間，(C)成分會產生熱交聯反應。又，與(B)成分之間，該聚醯亞胺前驅物所具有之羧基與(C)成分之間會產生交聯反應。Further, since the resin composition of the present embodiment contains the component (C), the cured film obtained by using the resin composition can be introduced into the crosslinked portion via a thermal reaction. That is, as described above, the (C) component generates a thermal crosslinking reaction with the component (A). Further, between the component (B) and the component (B), a crosslinking reaction occurs between the carboxyl group and the component (C) of the polyimide precursor.

經調整聚醯亞胺前驅物中之羧基含量時，可控制(B)成分與(C)成分之間的交聯反應，進而可控制(A)成分與(C)成分之間的交聯反應。其結果，於樹脂組成物所得之硬化膜全體中，經由熱反應則可實現有效率的交聯反應，經由導入交聯部位而可形成強固之硬化膜。When the carboxyl group content in the polyimide precursor is adjusted, the crosslinking reaction between the component (B) and the component (C) can be controlled, and the crosslinking reaction between the component (A) and the component (C) can be controlled. . As a result, in the entire cured film obtained from the resin composition, an efficient crosslinking reaction can be realized by a thermal reaction, and a strong cured film can be formed by introducing a crosslinking portion.

以下，將對(A)至(C)成分作詳細之說明。Hereinafter, the components (A) to (C) will be described in detail.

＜(A)成分＞<(A) component>

本實施形態之(A)成分為具有光二聚化部位及熱交聯部位之丙烯酸共聚物。(A)成分之丙烯酸共聚物之光二聚化部位為由疏水性基所形成，熱交聯部位為由親水性基所形成。以下，將列舉具體例示說明該些內容。The component (A) in the present embodiment is an acrylic copolymer having a photodimerization site and a thermal crosslinking site. The photodimerization site of the acrylic copolymer of the component (A) is formed of a hydrophobic group, and the thermally crosslinked site is formed of a hydrophilic group. Hereinafter, the contents will be specifically illustrated by enumeration.

本實施形態中，丙烯酸共聚物為使用由具有丙烯酸酯、甲基丙烯酸酯、苯乙烯等不飽和雙鍵之單體經聚合所得之共聚物。In the present embodiment, the acrylic copolymer is a copolymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylate, methacrylate or styrene.

(A)成分之具有光二聚化部位及熱交聯部位之丙烯酸共聚物(以下，亦稱為特定共聚物)，只要為具有該結構之丙烯酸共聚物即可，又，構成丙烯酸共聚物之高分子的主鏈之骨架及側鏈之種類等，並未有特別限定。The acrylic copolymer (hereinafter, also referred to as a specific copolymer) having a photodimerization site and a thermal crosslinking site of the component (A) may be an acrylic copolymer having the structure, and may constitute a high acrylic copolymer. The skeleton of the main chain of the molecule and the kind of the side chain are not particularly limited.

光二聚化部位為，經由光照射而生成二聚物之部位，其具體例如，桂皮醯基、查耳酮基、異丙苯基、蒽基等。該些之中，又以於可見光區域具有高透明性，與具有光二聚化反應性之桂皮醯基為佳。特佳之桂皮醯基的部分結構例如下述式[A1]與式[A2]所示。The photodimerization site is a site where a dimer is formed by light irradiation, and specifically, for example, a cinnamyl group, a chalcone group, a cumene group, a fluorenyl group or the like. Among these, it is preferable to have high transparency in the visible light region and cinnabar base having photodimerization reactivity. A partial structure of a particularly preferred cinnabar base is as shown in the following formula [A1] and formula [A2].

[化1][Chemical 1]

上述式中，X1表示氫原子、碳原子數1至18之烷基、苯基或聯苯基。其中，苯基及聯苯基分別可被鹵素原子及氰基中之任一者所取代。X2表示氫原子、氰基、碳原子數1至18之烷基、苯基、聯苯基或環己基。其中，碳原子數1至18之烷基、苯基、聯苯基或環己基可介由共價鍵、醚鍵、酯鍵、醯胺鍵或脲鍵予以鍵結。In the above formula, X 1 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. Among them, the phenyl group and the biphenyl group may be each substituted by either a halogen atom or a cyano group. X 2 represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group or a cyclohexyl group. Among them, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group or a cyclohexyl group may be bonded via a covalent bond, an ether bond, an ester bond, a guanamine bond or a urea bond.

R1、R2、R3及R4，各自獨立表示氫原子、碳原子數1至4之烷基、碳原子數1至4之烷氧基、鹵素原子、三氟甲基或氰基。R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group or a cyano group.

熱交聯部位為經由加熱而與交聯劑鍵結之部位，其具體例如，羥基、羧基或縮水甘油基等。The thermal crosslinking site is a site to which a crosslinking agent is bonded via heating, and specifically, for example, a hydroxyl group, a carboxyl group or a glycidyl group.

(A)成分之丙烯酸共聚物，其重量平均分子量以3,000至200,000為佳，以4,000至150,000為較佳，以5,000至100,000為最佳。重量平均分子量為超過200,000之過大物質時，會降低對溶劑之溶解性，而會有降低控制性之情形。又，重量平均分子量為未達3,000之過小物質時，其熱硬化時會造成硬化不足，而會有降低耐溶劑性及耐熱性之情形。The acrylic copolymer of the component (A) preferably has a weight average molecular weight of 3,000 to 200,000, preferably 4,000 to 150,000, and most preferably 5,000 to 100,000. When the weight average molecular weight is an excessively large substance exceeding 200,000, the solubility to the solvent is lowered, and the controllability is lowered. Further, when the weight average molecular weight is too small as less than 3,000, the hardening may cause insufficient hardening, and the solvent resistance and heat resistance may be lowered.

如上所述般，(A)成分之側鏈具有光二聚化部位及熱交聯部位之丙烯酸共聚物之合成方法，以將具有光二聚化部位之單體，與具有熱交聯部位之單體進行共聚合之方法為佳。As described above, the side chain of the component (A) has a method of synthesizing an acrylic copolymer having a photodimerization site and a thermal crosslinking site, and a monomer having a photodimerization site and a monomer having a thermal crosslinking site. The method of performing copolymerization is preferred.

具有光二聚化部位之單體，例如，具有桂皮醯基、查耳酮基、異丙苯基或蒽基等之單體等。該些之中，就可見光區域具有透明性，與具有良好光二聚化反應性之具有桂皮醯基的單體為佳。特別是以具有上述式[A1]或式[A2]所表示之結構的桂皮醯基的單體為佳。該單體之具體例，例如下述式[A3]與式[A4]所示。A monomer having a photodimerization site, for example, a monomer having a cinnamyl group, a chalcone group, a cumene group or a fluorenyl group. Among these, it is preferred that the visible light region has transparency and a monomer having a cinnamyl group having good photodimerization reactivity. In particular, a monomer having a cinnamyl group having the structure represented by the above formula [A1] or formula [A2] is preferred. Specific examples of the monomer are, for example, the following formula [A3] and formula [A4].

[化2][Chemical 2]

上述式中、X1表示氫原子、碳原子數1至18之烷基、苯基或聯苯基。其中，苯基及聯苯基分別可被鹵素原子及氰基中之任一者所取代。X2表示氫原子、氰基、碳原子數1至18之烷基、苯基、聯苯基或環己基。其中，碳原子數1至18之烷基、苯基、聯苯基及環己基可介由共價鍵、醚鍵、酯鍵、醯胺鍵或脲鍵予以鍵結。X3及X5，各自獨立表示單鍵、碳原子數1至20之伸烷基、芳香環基或脂環基。其中，碳原子數1至20之伸烷基可為分支狀或直鏈狀皆可。X4及X6表示聚合性基。該聚合性基之具體例，例如，丙烯醯基、甲基丙烯醯基、苯乙烯基、馬來醯亞胺基、丙烯酸醯胺基及甲基丙烯酸醯胺基等。In the above formula, X 1 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. Among them, the phenyl group and the biphenyl group may be each substituted by either a halogen atom or a cyano group. X 2 represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group or a cyclohexyl group. Among them, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group and a cyclohexyl group may be bonded via a covalent bond, an ether bond, an ester bond, a guanamine bond or a urea bond. X 3 and X 5 each independently represent a single bond, an alkylene group having 1 to 20 carbon atoms, an aromatic ring group or an alicyclic group. Among them, the alkylene group having 1 to 20 carbon atoms may be branched or linear. X 4 and X 6 represent a polymerizable group. Specific examples of the polymerizable group include, for example, an acrylonitrile group, a methacryl fluorenyl group, a styryl group, a maleimine group, a decyl amide group, and a decylamino group.

R1、R2、R3及R4，各自獨立表示氫原子、碳原子數1至4之烷基、碳原子數1至4之烷氧基、鹵素原子、三氟甲基或氰基。例如，4-(6-甲基丙烯氧己基-1-氧基)桂皮酸甲酯及6-(丙烯醯氧基)己基-3-(4-甲氧苯基)丙烯酸酯等。R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group or a cyano group. For example, methyl 4-(6-methylpropoxyhexyl-1-oxy) cinnamate and 6-(acryloxy)hexyl-3-(4-methoxyphenyl)acrylate.

具有熱交聯部位之單體，例如，2-羥丙烯酸乙酯、2-羥甲基丙烯酸乙酯、2-羥丙基丙烯酸酯、2-羥丙基甲基丙烯酸酯、4-羥丁基丙烯酸酯、4-羥丁基甲基丙烯酸酯、2,3-二羥丙基丙烯酸酯、2,3-二羥丙基甲基丙烯酸酯、二乙二醇單丙烯酸酯、二乙二醇單甲基丙烯酸酯、己內酯2-(丙烯醯氧基)乙基酯、己內酯2-(甲基丙烯醯氧基)乙基酯、聚(乙二醇)乙基醚丙烯酸酯、聚(乙二醇)乙基醚甲基丙烯酸酯、5-丙烯醯基氧代-6-羥基降冰片烯-2-朘酸酯-6-內酯及5-甲基丙烯醯氧代-6-羥基降冰片烯-2-朘酸酯-6-內酯等具有羥基之單體、丙烯酸、甲基丙烯酸、巴豆酸、單-(2-(丙烯醯氧基)乙基)苯二甲酸酯、單-(2-(甲基丙烯醯氧基)乙基)苯二甲酸酯、N-(羧基苯基)馬來醯亞胺、N-(羧基苯基)甲基丙烯酸醯胺及N-(羧基苯基)丙烯酸醯胺等具有羧基之單體、羥基苯乙烯、N-(羥基苯基)甲基丙烯酸醯胺、N-(羥基苯基)丙烯酸醯胺、N-(羥基苯基)馬來醯亞胺及N-(羥基苯基)馬來醯亞胺等具有酚性羥基之單體，以及縮水甘油基甲基丙烯酸酯及縮水甘油基丙烯酸酯等具有縮水甘油基之單體等。Monomer having a thermally crosslinked moiety, for example, ethyl 2-hydroxyacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl Acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethyl Acrylate, caprolactone 2-(acryloxy)ethyl ester, caprolactone 2-(methacryloxy)ethyl ester, poly(ethylene glycol) ethyl ether acrylate, poly(B) Glycol) ethyl ether methacrylate, 5-propenyl oxo-6-hydroxynorbornene-2-decanoate-6-lactone and 5-methyl propylene oxo-6-hydroxyl Monomer having a hydroxyl group such as borneol-2-phthalate-6-lactone, acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloxy)ethyl) phthalate, single -(2-(methacryloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylate amide and N-( Carboxyl group, hydroxystyrene, N-(hydroxyphenyl)methacrylate a monomer having a phenolic hydroxyl group such as N-(hydroxyphenyl)acrylic acid decylamine, N-(hydroxyphenyl)maleimide, and N-(hydroxyphenyl)maleimide, and a glycidyl group A monomer having a glycidyl group such as methacrylate or glycidyl acrylate.

又，本實施形態中，欲製得特定共聚物之際，除具有光二聚化部位及熱交聯部位(以下，亦稱為特定官能基)之單體以外，亦可與可與該單體共聚，但不具有特定官能基之單體合併使用。Further, in the present embodiment, in addition to a monomer having a photodimerization site and a thermal crosslinking site (hereinafter also referred to as a specific functional group), a specific copolymer may be used together with the monomer. Copolymers, but monomers having no specific functional groups, are used in combination.

不具有上述特定官能基之單體的具體例如，丙烯酸酯化合物、甲基丙烯酸酯化合物、馬來醯亞胺化合物、丙烯酸醯胺化合物、丙烯腈、馬來酸酐、苯乙烯化合物及乙烯基化合物等。該些之具體例如，下述內容等。但並不僅限定於該些內容之中。Specific examples of the monomer having no specific functional group as described above, for example, an acrylate compound, a methacrylate compound, a maleimide compound, a decylamine compound, acrylonitrile, maleic anhydride, a styrene compound, a vinyl compound, etc. . Specific examples thereof include the following. But it is not limited to this content.

丙烯酸酯化合物，例如，丙烯酸甲酯、丙烯酸乙酯、丙烯酸異丙酯、丙烯酸苄酯、丙烯酸萘酯、丙烯酸蒽酯、丙烯酸蒽甲酯、丙烯酸苯酯、丙烯酸縮水甘油酯、丙烯酸2,2,2-三氟乙酯、丙烯酸tert-丁酯、丙烯酸環己酯、丙烯酸異莰酯、丙烯酸2-甲氧乙酯、丙烯酸甲氧基三乙二醇酯、丙烯酸2-乙氧乙酯、丙烯酸2-胺基乙酯、丙烯酸四氫糠酯、丙烯酸3-甲氧基丁酯、丙烯酸2-甲基-2-金剛烷酯、丙烯酸2-丙基-2-金剛烷酯、丙烯酸8-甲基-8-三環癸酯及丙烯酸8-乙基-8-三環癸酯等。Acrylate compound, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, decyl acrylate, decyl acrylate, phenyl acrylate, glycidyl acrylate, acrylic acid 2, 2, 2-Trifluoroethyl ester, tert-butyl acrylate, cyclohexyl acrylate, isodecyl acrylate, 2-methoxyethyl acrylate, methoxy triethylene glycol acrylate, 2-ethoxyethyl acrylate, acrylic acid 2-Aminoethyl ester, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, Acrylic 8-A Base-8-tricyclodecyl ester and 8-ethyl-8-tricyclodecyl acrylate.

甲基丙烯酸酯化合物，例如，甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸異丙酯、甲基丙烯酸苄酯、甲基丙烯酸萘酯、甲基丙烯酸蒽酯、甲基丙烯酸蒽甲酯、甲基丙烯酸苯酯、甲基丙烯酸縮水甘油酯、甲基丙烯酸2,2,2-三氟乙酯、甲基丙烯酸tert-丁酯、甲基丙烯酸環己酯、甲基丙烯酸異莰酯、甲基丙烯酸2-甲氧乙酯、甲基丙烯酸甲氧基三乙二醇酯、甲基丙烯酸2-乙氧基乙酯、甲基丙烯酸2-胺基甲酯、甲基丙烯酸四氫糠基酯、甲基丙烯酸3-甲氧基丁酯、甲基丙烯酸2-甲基-2-金剛烷酯、甲基丙烯酸γ-丁內酯、甲基丙烯酸2-丙基-2-金剛烷酯、甲基丙烯酸8-甲基-8-三環癸酯及甲基丙烯酸8-乙基-8-三環癸酯等。A methacrylate compound, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, decyl methacrylate, methacrylic acid armor Ester, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate , 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydroanthracene methacrylate Base ester, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate And 8-methyl-8-tricyclodecyl methacrylate and 8-ethyl-8-tricyclodecyl methacrylate.

乙烯基化合物，例如，甲基乙烯基醚、苄基乙烯基醚、乙烯基萘、乙烯基卡必醇、烯丙基縮水甘油基醚、3-乙烯基-7-氧雜二[4.1.0]庚烷、1,2-環氧基-5-己烯及1,7-辛二烯單環氧化物等。Vinyl compounds, for example, methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbitol, allyl glycidyl ether, 3-vinyl-7-oxabis [4.1.0 Heptane, 1,2-epoxy-5-hexene and 1,7-octadiene monoepoxide, and the like.

苯乙烯化合物，例如，苯乙烯、甲基苯乙烯、氯基苯乙烯及溴基苯乙烯等。Styrene compounds, for example, styrene, methyl styrene, chlorostyrene, bromostyrene, and the like.

馬來醯亞胺化合物，例如，馬來醯亞胺、N-甲基馬來醯亞胺、N-苯基馬來醯亞胺及N-環己基馬來醯亞胺等。Maleic imine compounds, for example, maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

製得特定共聚物所使用之各單體之使用量，以全單體之合計量為基準，為25至90莫耳%之具有光二聚化部位之單體、10至75莫耳%之具有熱交聯部位之單體、0至65莫耳質量%之不具有特定官能基之單體為佳。具有光二聚化部位之單體之含量少於25莫耳%時，則難賦予高感度且具有良好之液晶配向性。又，具有熱交聯部位之單體之含量低於10莫耳%時，則難賦予充分之熱硬化性，且難以維持高感度之良好液晶配向性。The amount of each monomer used in the preparation of the specific copolymer is from 25 to 90 mol% of the monomer having a photodimerization site, and from 10 to 75 mol%, based on the total amount of all monomers. The monomer of the thermal crosslinking site, preferably 0 to 65 mol% of a monomer having no specific functional group. When the content of the monomer having a photodimerization site is less than 25 mol%, it is difficult to impart high sensitivity and good liquid crystal alignment. Moreover, when the content of the monomer having a thermal crosslinking portion is less than 10 mol%, it is difficult to impart sufficient thermosetting property, and it is difficult to maintain high liquid crystal alignment with high sensitivity.

本實施形態中，製得特定共聚物之方法並未有特別限定。例如，於存在有具有特定官能基之單體，與所期待之不具有特定官能基之單體，與聚合起始劑等之溶劑中，於50至110℃之溫度下進行聚合反應結果，即可製得特定共聚物。此時所使用之溶劑，只要可以溶解具有特定官能基之單體，與所期待之不具有特定官能基之單體，與聚合起始劑等之溶劑時，並未有特別限定。又，該溶劑於後述＜溶劑＞欄中亦有說明。In the present embodiment, the method for producing a specific copolymer is not particularly limited. For example, in the presence of a monomer having a specific functional group, a desired monomer having no specific functional group, and a polymerization initiator or the like, the polymerization reaction is carried out at a temperature of 50 to 110 ° C, that is, A specific copolymer can be obtained. The solvent to be used at this time is not particularly limited as long as it can dissolve a monomer having a specific functional group, a monomer having no specific functional group, and a solvent such as a polymerization initiator. Further, the solvent is also described in the <solvent> column described later.

依上述方法所得之特定共聚物，通常為溶解於溶劑所得溶液之狀態。The specific copolymer obtained by the above method is usually in the form of a solution obtained by dissolving in a solvent.

又，上述方法所得之特定共聚物之溶液，於攪拌下投入二乙基醚或水等後，使其再沈澱，將生成之沈澱物濾過‧洗淨後，於常壓或減壓下，進行常溫乾燥或加熱乾燥，而形成特定共聚物之粉體。經由前述操作結果，可去除與特定共聚物共存之聚合起始劑及未反應之單體，其結果，可得到精製之特定共聚物的粉體。於未能以一次之操作充分精製之情形，可將所得粉體再溶解於溶劑中，重複上述之操作即可。Further, the solution of the specific copolymer obtained by the above method is added to diethyl ether or water under stirring, and then reprecipitated, and the resulting precipitate is filtered, washed, and then subjected to normal pressure or reduced pressure. It is dried at room temperature or dried by heating to form a powder of a specific copolymer. As a result of the above operation, the polymerization initiator and the unreacted monomer which are present in the specific copolymer can be removed, and as a result, a powder of the purified specific copolymer can be obtained. In the case where the purification is not sufficiently performed in one operation, the obtained powder may be redissolved in a solvent, and the above operation may be repeated.

本實施之形態中，特定共聚物可使用粉體形態亦可，或，使用將精製之粉末再溶解於後述溶劑所得之溶液形態亦可。In the embodiment of the present invention, the specific copolymer may be in the form of a powder, or may be in the form of a solution obtained by redissolving the purified powder in a solvent to be described later.

又，本實施形態中，(A)成分之特定共聚物可為複數種特定共聚物之混合物。Further, in the present embodiment, the specific copolymer of the component (A) may be a mixture of a plurality of specific copolymers.

＜(B)成分＞<(B) component>

本實施形態中之(B)成分為聚醯亞胺前驅物。(B)成分之聚醯亞胺前驅物為具有芳香環部位者。為達成高雙折射率之目的，聚醯亞胺前驅物之中，又以具有下述式(1)所表示之結構單位的聚醯亞胺前驅物為佳。The component (B) in the present embodiment is a polyimine precursor. The polyimine precursor of the component (B) is one having an aromatic ring moiety. For the purpose of achieving high birefringence, it is preferred that the polyimine precursor has a polyimine precursor having a structural unit represented by the following formula (1).

[化3][Chemical 3]

上述式(1)中，A1為至少含有1個由1至3個脂環結構或苯環直接鍵結之骨架、萘環骨架及蒽環骨架等具有芳香環部位之結構的有機基，B1為至少含有1個含脂環結構或三氟甲基或三氟甲基之基的苯環等的具有芳香環部位之結構的有機基，R5、R6各自獨立表示氫原子或碳原子數1至7之有機基。其中，式(1)中，至少A1或B1之任一者為，含有具有芳香環部位之結構的有機基。In the above formula (1), A 1 is an organic group having at least one structure having an aromatic ring moiety such as a skeleton which is directly bonded to one to three alicyclic structures or a benzene ring, a naphthalene ring skeleton, and an anthracene ring skeleton, B 1 is an organic group having a structure having an aromatic ring moiety such as a benzene ring containing an alicyclic structure or a trifluoromethyl group or a trifluoromethyl group, and R 5 and R 6 each independently represent a hydrogen atom or a carbon atom. An organic group of 1 to 7. In the formula (1), at least one of A 1 or B 1 is an organic group having a structure having an aromatic ring moiety.

式(1)中之A1的具體例如，含有下述表1所示T1至T9所表示之結構的有機基等。但，並不僅限定於該內容中。Specific examples of A 1 in the formula (1) include an organic group or the like having a structure represented by T1 to T9 shown in Table 1 below. However, it is not limited to this content.

本實施形態中，式(1)中之B1為至少含有1個具有脂環結構或含三氟甲基或三氟甲基之基的苯環的有機基。其中，具有脂環結構或含三氟甲基或三氟甲基之基的苯環的有機基之具體例如，下述表2所示S1至S7所表示之有機基等。In the present embodiment, B 1 in the formula (1) is an organic group containing at least one benzene ring having an alicyclic structure or a trifluoromethyl group or a trifluoromethyl group. Specific examples of the organic group of the benzene ring having an alicyclic structure or a trifluoromethyl group or a trifluoromethyl group are, for example, the organic groups represented by S1 to S7 shown in Table 2 below.

本實施形態中，(B)成分之聚醯亞胺前驅物，可含有上述式(1)所表示之結構單位以外之其他結構單位。其中，其他之結構單位並未有特別之限定。又，亦可含有1種或複數種式(1)所表示之結構單位以外之結構單位。In the present embodiment, the polyimine precursor of the component (B) may contain other structural units than the structural unit represented by the above formula (1). Among them, other structural units are not particularly limited. Further, it may contain one or more structural units other than the structural unit represented by the formula (1).

(B)成分之聚醯亞胺前驅物的重量平均分子量為1000至100000，較佳為1500至60000。聚醯亞胺前驅物之重量平均分子量小於1000時，會有降低耐溶劑性而減低配向感度之情形。又，聚醯亞胺前驅物之重量平均分子量超過100000時，因溶液之黏度過高，而會使控制性降低。The polyimine precursor of the component (B) has a weight average molecular weight of from 1,000 to 100,000, preferably from 1,500 to 60,000. When the weight average molecular weight of the polyimide precursor is less than 1,000, the solvent resistance is lowered to reduce the alignment sensitivity. Further, when the weight average molecular weight of the polyimide precursor exceeds 100,000, the viscosity of the solution is too high, and the controllability is lowered.

＜(B)成分之製造方法＞<Method for producing (B) component>

本實施形態中，(B)成分之聚醯亞胺前驅物為由四羧酸二酐與二胺化合物經共聚合而製得。In the present embodiment, the polyimine precursor of the component (B) is obtained by copolymerizing a tetracarboxylic dianhydride and a diamine compound.

四羧酸二酐，以至少含有1個脂環結構之四羧酸二酐、至少含有1個由1至3個苯環直接鍵結之結構的四羧酸二酐，或或至少含有1個萘環之四羧酸二酐為佳。a tetracarboxylic dianhydride having a tetracarboxylic dianhydride containing at least one alicyclic structure, a tetracarboxylic dianhydride having at least one structure directly bonded by 1 to 3 benzene rings, or at least one A naphthalene ring tetracarboxylic dianhydride is preferred.

上述酸二酐之具體例，例如，苯均四酸二酐、2,3,6,7-萘四羧酸二酐、1,2,5,6-萘四羧酸二酐、1,4,5,8-萘四羧酸二酐、2,3,6,7-蒽四羧酸二酐、1,2,5,6-蒽四羧酸二酐、3,3’,4,4’-聯苯基四羧酸二酐、2,2’,3,3’-聯苯基四羧酸二酐及2,3,3’,4’-聯苯基四羧酸二酐、1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐、1,2,4,5-環己烷四羧酸二酐、雙環[3.3.0]辛烷-2,4,6,8-四羧酸二酐等。Specific examples of the above acid dianhydride include, for example, pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4 ,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-nonanetetracarboxylic dianhydride, 1,2,5,6-nonanedicarboxylic dianhydride, 3,3',4,4 '-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride and 2,3,3',4'-biphenyltetracarboxylic dianhydride, 1 , 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, Bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride or the like.

本實施形態中，四羧酸二酐成分可含有上述以外之其他的四羧酸二酐。該情形中，其他之四羧酸二酐可含有1種，或複數種皆可。In the present embodiment, the tetracarboxylic dianhydride component may contain other tetracarboxylic dianhydrides than the above. In this case, the other tetracarboxylic dianhydride may be contained in one type or in a plurality of types.

其他的四羧酸二酐之具體例，例如，3,3’,4,4’-二苯甲酮四羧酸二酐、2,3,3’,4’-二苯甲酮四羧酸二酐、雙(3,4-二羧基苯基)甲烷二酐、雙(3,4-二羧基苯基)醚二酐、雙(3,4-二羧基苯基)碸二酐、2,2-雙(3,4-二羧基苯基)丙烷二酐、2,2-雙(3,4-二羧基苯基)六氟丙烷二酐、2,5-二羧甲基對苯二甲酸二酐、4,6-二羧甲基異苯二甲酸二酐、4-(2,5-二氧雜四氫-3-呋喃基)苯二甲酸酐、1,4-雙(2,5-二氧雜四氫-3-呋喃基)苯、1,4-雙(2,6-二氧雜四氫-4-吡喃基)苯、1,4-雙(2,5-二氧雜四氫-3-甲基-3-呋喃基)苯、1,4-雙(2,6-二氧雜四氫-4-甲基-4-吡喃基)苯、1,2-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-四甲基-1,2,3,4-環丁烷四羧酸二酐、2,3,4,5-四氫呋喃四羧酸二酐、2,3,5-三羧基環戊基乙酸二酐、4-(2,5-二氧雜四氫-3-呋喃基)-環己烷-1,2-二羧酸酐、四環[2,2,1,1,1]癸烷-2,3,7,8-四羧酸二酐、5-(2,5-二氧雜四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、雙環[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、3,3’,4,4’-二環己基四羧酸二酐、2,3,5,6-降冰片烷四羧酸二酐、3,5,6-三羧基降冰片烷-2-乙酸二酐、三環[4.2.1.02,5]壬烷-3,4,7,8-四羧酸二酐、四環[4.4.1.02,5.07,10]十一烷-3,4,8,9-四羧酸二酐、六環[6.6.0.12,7.03,6.19,14.010,13]十六烷-4,5,11,12-四羧酸二酐、1,4-雙(2,5-二氧雜四氫-3-呋喃基)己烷、1,4-雙(2,6-二氧雜四氫-4-吡喃基)己烷、3,4-二羧-1,2,3,4-四氫-1-萘琥珀酸二酐、1,2-二苯基-1,2,3,4-環丁烷四羧酸二酐及1,2,3,4,5,6,7,8-八氫-2,3,6,7-蒽四羧酸二酐等。Specific examples of other tetracarboxylic dianhydrides, for example, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic acid Dihydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, 2, 2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,5-dicarboxymethyl terephthalic acid Dihydride, 4,6-dicarboxymethylisophthalic dianhydride, 4-(2,5-dioxatetrahydro-3-furanyl) phthalic anhydride, 1,4-double (2,5 -dioxatetrahydro-3-furanyl)benzene, 1,4-bis(2,6-dioxatetrahydro-4-pyranyl)benzene, 1,4-bis(2,5-dioxo) Heterotetrahydro-3-methyl-3-furanyl)benzene, 1,4-bis(2,6-dioxatetrahydro-4-methyl-4-pyranyl)benzene, 1,2-di Methyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3 , 4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl Acetic acid dianhydride, 4-(2,5-dioxatetrahydro-3-furanyl)-cyclohexane-1,2-dicarboxylic anhydride, tetracyclo[2,2,1,1,1]decane -2,3,7,8-tetracarboxylic acid Dihydride, 5-(2,5-dioxatetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]oct-7 -ene-2,3,5,6-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5,6-norbornanetetracarboxylic acid Dihydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, tricyclo[4.2.1.0 2,5 ]decane-3,4,7,8-tetracarboxylic dianhydride, tetracyclic [4.4.1.0 2,5 .0 7,10 ] undecane-3,4,8,9-tetracarboxylic dianhydride, hexacyclo[6.6.0.1 2,7 .0 3,6 .1 9,14 .0 10,13 ]hexadecane-4,5,11,12-tetracarboxylic dianhydride, 1,4-bis(2,5-dioxatetrahydro-3-furanyl)hexane, 1, 4-bis(2,6-dioxatetrahydro-4-pyranyl)hexane, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1 ,2-diphenyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2,3,4,5,6,7,8-octahydro-2,3,6,7 - 蒽 tetracarboxylic dianhydride and the like.

作為(B)成分之聚醯亞胺前驅物之原料的二胺成分，以含有脂環結構或三氟甲基之二胺化合物為佳，亦可併用其以外之二胺化合物。該二胺化合物之具體例，例如，1,4-二胺基環己烷、1,3-二胺基環己烷、雙(4-胺基環己基)甲烷、雙(4-胺基-3-甲基環己基)甲烷、1,4’-雙環己基二胺、2,2’-三氟甲基-4,4’-二胺基聯苯基、3,3’-三氟甲基-4,4’-二胺基聯苯基、4,4’-二胺基二苯基甲烷、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、2,2-雙(3-胺基-4-甲基苯基)丙烷、2,2-雙(4-胺基苯基)六氟丙烷、2,2-雙(3-胺基苯基)六氟丙烷、2,2-雙(3-胺基-4-甲基苯基)六氟丙烷及1,3-雙(4-胺基苯氧基)丙烷等。The diamine component which is a raw material of the polyimine precursor of the component (B) is preferably a diamine compound having an alicyclic structure or a trifluoromethyl group, and may be used in combination with a diamine compound other than the diamine compound. Specific examples of the diamine compound are, for example, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, bis(4-aminocyclohexyl)methane, bis(4-amino group- 3-methylcyclohexyl)methane, 1,4'-dicyclohexyldiamine, 2,2'-trifluoromethyl-4,4'-diaminobiphenyl, 3,3'-trifluoromethyl -4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-aminophenyl) Hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, and 1,3-bis(4-aminophenoxy)propane.

本實施形態中，除上述二胺化合物以外，亦可併用1種或複數種其他之二胺化合物使用。In the present embodiment, in addition to the above diamine compound, one type or a plurality of other diamine compounds may be used in combination.

其他之二胺化合物，例如，雙(4-胺基苯基)碸、雙(3-胺基苯基)碸、雙(4-胺基-3-羧基苯基)碸、雙(4-胺基-3,5-二羧基苯基)碸、雙[4-(4-胺基-3-羧基苯氧基)苯基]碸、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]碸、雙(3-胺基-4-羥基苯基)碸、雙(4-胺基-3-羥基苯基)碸、雙(4-胺基-3,5-二羥基苯基)碸、3,3’-二胺基-4,4’-二氯基二苯基碸、p-伸苯基二胺、m-伸苯基二胺、2,4-二胺基甲苯、2,5-二胺基甲苯、2,6-二胺基甲苯、2,4-二甲基-1,3-二胺基苯、2,5-二甲基-1,4-二胺基苯、2,3,5,6-四甲基-1,4-二胺基苯、2,4-二胺基酚、2,5-二胺基酚、4,6-二胺基間苯二酚、2,5-二胺基苯甲酸、3,5-二胺基苯甲酸、N,N-二烯丙基-2,4-二胺基苯胺、N,N-二烯丙基-2,5-二胺基苯胺、4-胺基苄基胺、3-胺基苄基胺、2-(4-胺基苯基)乙基胺、2-(3-胺基苯基)乙基胺、1,5-萘二胺、2,7-萘二胺、4,4’-二胺基聯苯基、3,4’-二胺基聯苯基、3,3’-二胺基聯苯基、2,2’-二甲基-4,4’-二胺基聯苯基、3,3’-二甲基-4,4’-二胺基聯苯基、3,3’-二甲氧基-4,4’-二胺基聯苯基、3,3’-二羥基-4,4’-二胺基聯苯基、3,3’-二羧-4,4’-二胺基聯苯基、3,3’-二氟-4,4’-二胺基聯苯基、3,3’-二胺基二苯基甲烷、3,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基醚、3,3’-二胺基二苯基醚、3,4’-二胺基二苯基醚、4,4’-二胺基二苯基胺、3,3’-二胺基二苯基胺、3,4’-二胺基二苯基胺、N-甲基(4,4’-二胺基二苯基)胺、N-甲基(3,3’-二胺基二苯基)胺、N-甲基(3,4’-二胺基二苯基)胺、4,4’-二胺基二苯甲酮、3,3’-二胺基二苯甲酮、3,4’-二胺基二苯甲酮、4,4’-二胺基苯甲醯苯胺、1,2-雙(4-胺基苯基)乙烷、1,2-雙(3-胺基苯基)乙烷、4,4’-二胺基二苯乙炔、1,3-雙(4-胺基苯基)丙烷、1,3-雙(3-胺基苯基)丙烷、2,2-雙(4-胺基苯基)丙烷、2,2-雙(3-胺基苯基)丙烷、1,4-雙(4-胺基苯氧基)丁烷、1,5-雙(4-胺基苯氧基)戊烷、1,6-雙(4-胺基苯氧基)己烷、1,7-雙(4-胺基苯氧基)庚烷、1,8-雙(4-胺基苯氧基)辛烷、1,9-雙(4-胺基苯氧基)壬烷、1,10-雙(4-胺基苯氧基)癸烷、1,11-雙(4-胺基苯氧基)十一烷、1,12-雙(4-胺基苯氧基)十二烷、雙(4-胺基苯基)丙烷二基體(dioate)、雙(4-胺基苯基)丁烷二基體、雙(4-胺基苯基)戊烷二基體、雙(4-胺基苯基)己烷二基體、雙(4-胺基苯基)庚烷二基體、雙(4-胺基苯基)辛烷二基體、雙(4-胺基苯基)壬烷二基體、雙(4-胺基苯基)癸烷二基體、1,4-雙(4-胺基苯基)苯、1,3-雙(4-胺基苯基)苯、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(4-胺基苄基)苯、1,3-雙(4-胺基苄基)苯、雙(4-胺基苯基)對苯二甲酸酯、雙(3-胺基苯基)對苯二甲酸酯、雙(4-胺基苯基)間苯二甲酸酯、雙(3-胺基苯基)間苯二甲酸酯、1,4-伸苯基雙[(4-胺基苯基)甲酮]、1,4-伸苯基雙[(3-胺基苯基)甲酮]、1,3-伸苯基雙[(4-胺基苯基)甲酮]、1,3-伸苯基雙[(3-胺基苯基)甲酮]、1,4-伸苯基雙(4-胺基苯甲酸酯)、1,4-伸苯基雙(3-胺基苯甲酸酯)、1,3-伸苯基雙(4-胺基苯甲酸酯)、1,3-伸苯基雙(3-胺基苯甲酸酯)、N,N’-(1,4-伸苯基)雙(4-胺基苯併醯胺)、N,N’-(1,3-伸苯基)雙(4-胺基苯併醯胺)、N,N’-(1,4-伸苯基)雙(3-胺基苯併醯胺)、N,N’-(1,3-伸苯基)雙(3-胺基苯併醯胺)、雙(4-胺基苯基)對苯二甲醯胺、雙(3-胺基苯基)對苯二甲醯胺、雙(4-胺基苯基)異苯二甲醯胺、雙(3-胺基苯基)異苯二甲醯胺、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、4,4’-雙(4-胺基苯氧基)二苯基碸、2,6-二胺基砒啶、2,4-二胺基砒啶、2,4-二胺基-1,3,5-三嗪、2,6-二胺基二苯併呋喃、2,7-二胺基二苯併呋喃、3,6-二胺基二苯併呋喃、2,6-二胺基卡必醇、2,7-二胺基卡必醇、3,6-二胺基卡必醇、2,4-二胺基-6-異丙基-1,3,5-三嗪、2,5-雙(4-胺基苯基)-1,3,4-氧雜二唑、1,3-二胺基丙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基己烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷、1,11-二胺基十一烷及1,12-二胺基十二烷等。Other diamine compounds, for example, bis(4-aminophenyl)anthracene, bis(3-aminophenyl)anthracene, bis(4-amino-3-carboxyphenyl)anthracene, bis(4-amine 3-,5-dicarboxyphenyl)anthracene, bis[4-(4-amino-3-carboxyphenoxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl碸, bis[4-(3-aminophenoxy)phenyl]indole, bis(3-amino-4-hydroxyphenyl)indole, bis(4-amino-3-hydroxyphenyl)indole , bis(4-amino-3,5-dihydroxyphenyl)anthracene, 3,3'-diamino-4,4'-dichlorodiphenylanthracene, p-phenylenediamine, m - phenyldiamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,4-dimethyl-1,3-diaminobenzene , 2,5-dimethyl-1,4-diaminobenzene, 2,3,5,6-tetramethyl-1,4-diaminobenzene, 2,4-diaminophenol, 2, 5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, N,N-diallyl-2, 4-Diaminoaniline, N,N-diallyl-2,5-diaminoaniline, 4-aminobenzylamine, 3-aminobenzylamine, 2-(4-aminophenyl Ethylamine, 2-(3-aminophenyl)ethylamine, 1,5-naphthalenediamine, 2,7-naphthalenediamine, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'- Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4' -diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 3, 3'-Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenyl Amine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl (3,4'- Diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4, 4'-Diaminobenzimidamide, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 4,4'-diamine Diphenylacetylene, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 2,2-bis(4-amine Phenyl)propane, 2,2-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy) Pentane, 1,6-bis(4-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,8-bis(4-aminophenoxyl) Octane, 1,9-bis(4-aminophenoxy)decane, 1,10-bis(4-aminophenoxy)decane, 1,11-bis(4-aminobenzene Oxy) undecane, 1,12-bis(4-aminophenoxy)dodecane, bis(4-aminophenyl)propane diphenyl (dioate), bis(4-aminophenyl) Butane dibasic, bis(4-aminophenyl)pentane dibase, bis(4-aminophenyl)hexanediyl, bis(4-aminophenyl)heptane diyl, bis (4) -aminophenyl)octanediyl, bis(4-aminophenyl)decanediyl, bis(4-aminophenyl)decanediyl, 1,4-bis(4-aminobenzene) Benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene , 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminobenzyl)benzene, bis(4-aminophenyl)terephthalate, double (3) -aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl) Phthalate, 1,4-phenylene bis[(4-aminophenyl)methanone], 1,4-phenylene bis[(3-aminophenyl)methanone], 1, 3-phenylphenylbis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4-phenylene bis(4) -aminobenzoic acid ester), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3 - phenyl bis(3-aminobenzoate), N,N'-(1,4-phenylene) bis(4-aminobenzophthalamide), N,N'-(1, 3-phenylene) bis(4-aminobenzoguanamine), N,N'-(1,4-phenylene)bis(3-aminobenzophthalamide), N,N'-( 1,3-phenylene)bis(3-aminobenzophthalamide), bis(4-aminophenyl)terephthalamide, bis(3-aminophenyl)terephthalic acid Amine, bis(4-aminophenyl)isophthalamide, bis(3-aminophenyl)isophthalamide, 2,2-bis[4-(4-aminophenoxy) Phenyl]propane, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,6-diaminoacridine, 2,4-diaminoacridine, 2,4- Diamino-1,3,5-triazine, 2,6-diaminodibenzofuran, 2,7-diaminodibenzofuran, 3,6-diaminodibenzofuran, 2 ,6-diaminocarbamide, 2,7- Amino carbitol, 3,6-diaminocarbitol, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis(4-amino group Phenyl)-1,3,4-oxadiazole, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diamine Hexyl, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diamine 1,10-decane and 1,12-diaminododecane.

上述(B)成分之聚醯亞胺前驅物中，四羧酸二酐之合計量(酸成分之合計量)與二胺化合物之合計量(二胺成分之合計量)的組成比、即，〈二胺化合物之合計莫耳數〉/〈四羧酸二酐化合物之合計莫耳數〉以0.5至1.5為佳。與通常之聚縮合反應相同般，此莫耳比越接近1時，其所生成之聚醯亞胺前驅物之聚合度越大，故分子量為增加。The composition ratio of the total amount of the tetracarboxylic dianhydride (the total amount of the acid components) to the total amount of the diamine compounds (the total amount of the diamine components) of the polyimine precursor of the component (B), that is, <Total Molar Number of Diamine Compound> / <Total Molar Number of Tetracarboxylic Acid dianhydride Compound> It is preferably from 0.5 to 1.5. As in the case of the usual polycondensation reaction, the closer the molar ratio is to 1, the greater the degree of polymerization of the polyimine precursor formed, and the molecular weight is increased.

(B)成分之聚醯亞胺前驅物之末端，受到酸成分與二胺成分之組成比而產生變化，故於本實施形態中並未有特別之限定。The terminal of the polyimine precursor of the component (B) is changed by the composition ratio of the acid component to the diamine component, and thus is not particularly limited in the embodiment.

使用過量二胺成分進行聚合之情形中，會使末端胺基與羧酸酐進行反應，而可保護末端胺基。該些羧酸酐之例如，苯二甲酸酐、偏苯三甲酸酐、馬來酸酐、萘二甲酸酐、氫化苯二甲酸酐、甲基-5-降冰片烯-2,3-二羧酸酐、衣康酸酐及四氫苯二甲酸酐等。In the case where polymerization is carried out using an excess of the diamine component, the terminal amine group is reacted with the carboxylic acid anhydride to protect the terminal amine group. Examples of the carboxylic acid anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, and clothing. Kang anhydride and tetrahydrophthalic anhydride.

上述(B)成分之聚醯亞胺前驅物之製造中，酸成分與二胺成分與之反應溫度可於-20至150℃，較佳為於-5至100℃之任意溫度內進行選擇。例如，反應溫度設定為5至40℃，反應時間設定為1至48小時，即可製得聚醯亞胺前驅物。又，末端胺基被酸酐所保護之情形的反應溫度，可於-20至150℃，較佳為-5至100℃之任意溫度內進行選擇。In the production of the polyimine precursor of the above component (B), the reaction temperature of the acid component and the diamine component may be selected at any temperature of from -20 to 150 ° C, preferably from -5 to 100 ° C. For example, the reaction temperature is set to 5 to 40 ° C, and the reaction time is set to 1 to 48 hours to prepare a polyimide precursor. Further, the reaction temperature in the case where the terminal amine group is protected by an acid anhydride can be selected at any temperature of from -20 to 150 ° C, preferably from -5 to 100 ° C.

上述酸成分與二胺成分與之反應，通常為於溶劑中進行。此時所使用之溶劑，例如，N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮、N-乙烯基吡咯啶酮、N-甲基己內醯胺、二甲基亞碸、四甲基脲、二甲基碸、六甲基亞碸、m-甲酚、γ-丁內酯、3-甲氧基丙酸甲酯、2-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、2-甲氧基丙酸乙酯、3-乙氧基丙酸乙酯、2-乙氧基丙酸乙酯、乙二醇二甲基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇甲基乙基醚、丙二醇二甲基醚、二丙二醇二甲基醚、乙二醇單甲基醚、乙二醇單乙基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、丙二醇單甲基醚、丙二醇單乙基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、環己酮、甲基乙基酮、甲基異丁酮及2-庚酮等。該些可單獨使用或混合使用皆可。此外，即使不會溶解聚醯亞胺前驅物之溶劑，只要不會析出經聚合反應所生成之聚醯亞胺前驅物之範圍時，可與上述溶劑混合使用。The acid component and the diamine component are reacted therewith, usually in a solvent. The solvent used at this time, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-A Benzoamine, dimethyl hydrazine, tetramethyl urea, dimethyl hydrazine, hexamethyl hydrazine, m-cresol, γ-butyrolactone, methyl 3-methoxypropionate, 2 Methyl methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate, B Glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene Alcohol 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, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone and 2-heptanone. These may be used singly or in combination. Further, even if the solvent of the polyimide precursor is not dissolved, it can be used in combination with the above solvent as long as it does not precipitate the range of the polyimide precursor formed by the polymerization reaction.

依上述方法所得之含有聚醯亞胺前驅物之溶液，可無須加工下製作熱硬化膜形成用樹脂組成物。又，聚醯亞胺前驅物亦可於水、甲醇及乙醇等貧溶劑中沈澱單離後回收使用。The solution containing the polyimide precursor obtained by the above method can be used to form a resin composition for forming a thermosetting film without processing. Further, the polyimide precursor can also be recovered after being precipitated in a poor solvent such as water, methanol or ethanol.

＜(C)成分＞<(C) component>

本實施形態之(C)成分為交聯劑。該交聯劑為可使(A)成分與(B)成分交聯之成份。The component (C) in the present embodiment is a crosslinking agent. The crosslinking agent is a component which can crosslink the component (A) and the component (B).

(C)成分之交聯劑，例如，環氧化合物、羥甲基化合物或異氰酸酯化合物等，較佳為具有2個以上羥甲基或烷氧基羥甲基的羥甲基化合物。The crosslinking agent of the component (C), for example, an epoxy compound, a methylol compound or an isocyanate compound, is preferably a methylol compound having two or more methylol groups or alkoxymethylol groups.

具體而言，例如甲氧基甲基化乙炔脲、甲氧基甲基化苯胍胺及甲氧基甲基化三聚氰胺等之化合物等。又，例如，六甲氧基甲基三聚氰胺、四甲氧基甲基苯胍胺、1,3,4,6-四(丁氧甲基)乙炔脲、1,3,4,6-四(羥基甲基)乙炔脲、1,3-雙(羥基甲基)脲、1,1,3,3-四(丁氧甲基)脲、1,1,3,3-四(甲氧基甲基)脲、1,3-雙(羥基甲基)-4,5-二羥基-2-四氫咪唑酮及1,3-雙(甲氧基甲基)-4,5-二甲氧基-2-四氫咪唑酮等。此外，市售品例如，日本科技行業(股)製甲氧基甲基型三聚氰胺化合物(商品名賽麥爾300、賽麥爾301、賽麥爾303、賽麥爾350)、丁氧甲基型三聚氰胺化合物(商品名麥克特506、麥克特508)、乙炔脲化合物(商品名賽麥爾1170、保達靈1174)等之化合物、甲基化脲樹脂(商品名UFR65)、丁基化脲樹脂(商品名UFR300、U-VAN10S60、U-VAN10R、U-VAN11HV)及DIC(股)製脲/甲醛系樹脂(高縮合型，商品名倍可明J-300S、倍可明P-955、倍可明N)等。此外，該些胺基之氫原子被羥甲基或烷氧基甲基所取代之三聚氰胺化合物、脲化合物、乙炔脲化合物及苯胍胺化合物經縮合所得之化合物亦可。例如，美國特許6,323,310號所記載之由三聚氰胺化合物(商品名賽麥爾303)與苯胍胺化合物(商品名賽麥爾1123)所製造之高分子量之化合物等。Specific examples thereof include compounds such as methoxymethylated acetylene urea, methoxymethylated benzoguanamine, and methoxymethylated melamine. Also, for example, hexamethoxymethylmelamine, tetramethoxymethylbenzamine, 1,3,4,6-tetrakis(butoxymethyl)acetyleneurea, 1,3,4,6-tetra(hydroxyl Methyl)acetylene urea, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetra(methoxymethyl) Urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-tetrahydroimidazolidone and 1,3-bis(methoxymethyl)-4,5-dimethoxy- 2-tetrahydroimidazolium and the like. In addition, commercially available products such as methoxymethyl melamine compounds (trade names Saimer 300, Semel 301, Saimer 303, Saimer 350), butoxymethyl groups, are manufactured by the Japanese technology industry. a compound such as a melamine compound (trade name: McTea 506, McTerm 508), an acetylene urea compound (trade name: Semel 1170, Paulin 1174), a methylated urea resin (trade name UFR65), butylated urea Resin (trade name UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV) and DIC (stock) urea/formaldehyde resin (high condensation type, trade name Becker J-300S, Beckham P-955, Beckham N) and so on. Further, a compound obtained by condensing a melamine compound, a urea compound, an acetylene urea compound, and a benzoguanamine compound in which a hydrogen atom of the amine group is substituted with a methylol group or an alkoxymethyl group may also be used. For example, a high molecular weight compound produced by a melamine compound (trade name Saimer 303) and a benzoguanamine compound (trade name Saimel 1123) described in U.S. Patent No. 6,323,310.

又，(C)成分，亦可使用被N-羥基甲基丙烯酸醯胺、N-甲氧基甲基甲基丙烯酸醯胺、N-乙氧基甲基丙烯酸醯胺、N-丁氧甲基甲基丙烯酸醯胺等羥基甲基或烷氧基甲基所取代之丙烯酸醯胺化合物或甲基丙烯酸醯胺化合物所製造之聚合物。該些聚合物，例如，聚(N-丁氧甲基丙烯酸醯胺)、N-丁氧甲基丙烯酸醯胺與苯乙烯之共聚物、N-羥基甲基甲基丙烯酸醯胺與甲基丙烯酸甲酯之共聚物、N-乙氧基甲基甲基丙烯酸醯胺與苄基甲基丙烯酸酯之共聚物，及N-丁氧甲基丙烯酸醯胺與苄基甲基丙烯酸酯與2-羥丙基甲基丙烯酸酯之共聚物等。該些聚合物之重量平均分子量，例如1,000至500,000，或例如2,000至200,000，或，3,000至150,000，或，3,000至50,000。Further, as the component (C), N-hydroxymethyl methacrylate, N-methoxymethyl methacrylate, N-ethoxymethyl decylamine or N-butoxymethyl may also be used. A polymer produced by a decylamine compound or a methacrylic acid methacrylate compound substituted with a hydroxymethyl group such as decylamine methacrylate or an alkoxymethyl group. Such polymers, for example, poly(N-butoxymethyl decyl amide), copolymer of N-butoxy methacrylate and styrene, N-hydroxymethyl methacrylate and methacrylic acid Copolymer of methyl ester, copolymer of N-ethoxymethyl methacrylate and benzyl methacrylate, and N-butoxy methacrylate and benzyl methacrylate and 2-hydroxyl a copolymer of propyl methacrylate or the like. The weight average molecular weight of the polymers is, for example, from 1,000 to 500,000, or such as from 2,000 to 200,000, or from 3,000 to 150,000, or from 3,000 to 50,000.

以上所例示之(C)成分之交聯劑，可單獨或將2種以上組合使用。The crosslinking agent of the component (C) exemplified above may be used alone or in combination of two or more.

本實施形態之樹脂組成物中，基於(A)成分之至少具有光二聚化部位及熱交聯部位之丙烯酸共聚物，與(B)成分之聚醯亞胺前驅物之合計量100質量份，(C)成分之交聯劑的含量以10至100質量份為佳。該比例低於10質量份時，會降低樹脂組成物所得之硬化膜的耐溶劑性或耐熱性，而會降低光配向時之感度。又，大於100質量份時，除降低光配向性以外，也會有降低保存安定性之疑慮。In the resin composition of the present embodiment, the total amount of the acrylic copolymer having at least the photodimerization site and the thermal crosslinking site of the component (A) and the polyamidimide precursor of the component (B) is 100 parts by mass. The content of the crosslinking agent of the component (C) is preferably from 10 to 100 parts by mass. When the ratio is less than 10 parts by mass, the solvent resistance or heat resistance of the cured film obtained by the resin composition is lowered, and the sensitivity at the time of photoalignment is lowered. Further, when it is more than 100 parts by mass, in addition to lowering the optical alignment, there is a fear that the storage stability is lowered.

＜(D)成分＞<(D) component>

本實施形態之樹脂組成物中，(D)成分可含有酸或熱酸發生劑。該(D)成分，就促進本實施形態之樹脂組成物的熱硬化性等觀點為有效者。In the resin composition of the present embodiment, the component (D) may contain an acid or a thermal acid generator. The component (D) is effective in promoting the thermosetting property of the resin composition of the present embodiment.

(D)成分之酸或熱酸發生劑，為含有磺酸基之化合物、鹽酸或其鹽以及預燒焙或後燒焙時會熱分解而產生酸之化合物，即，只要於80至250℃熱分解而產生酸之化合物時，並未有特別限定。該化合物，例如，鹽酸、甲烷磺酸、乙烷磺酸、丙烷磺酸、丁烷磺酸、戊烷磺酸、辛烷磺酸、苯磺酸、p-甲苯磺酸、樟腦烷磺酸、三氟甲烷磺酸、p-酚磺酸、2-萘磺酸、1,3,5-三甲苯磺酸、p-甲苯-2-磺酸、m-甲苯-2-磺酸、4-乙基苯磺酸、1H,1H,2H,2H-全氟辛烷磺酸、全氟(2-乙氧基乙烷)磺酸、五氟乙烷磺酸、七氟丁烷-1-磺酸、十二烷基苯磺酸等之磺酸或其水和物或鹽等。The acid or thermal acid generator of the component (D) is a compound containing a sulfonic acid group, hydrochloric acid or a salt thereof, and a compound which is thermally decomposed during calcination or post-baking to produce an acid, that is, as long as it is at 80 to 250 ° C. The compound which thermally decomposes to generate an acid is not specifically limited. The compound, for example, hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, decanoic acid, Trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, 1,3,5-trimethylbenzenesulfonic acid, p-toluene-2-sulfonic acid, m-toluene-2-sulfonic acid, 4-B Benzobenzenesulfonic acid, 1H, 1H, 2H, 2H-perfluorooctane sulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, heptafluorobutane-1-sulfonic acid a sulfonic acid such as dodecylbenzenesulfonic acid or a water or a salt thereof.

經由熱而發生酸之化合物，例如，雙(甲苯磺醯氧基)乙烷、雙(甲苯磺醯氧基)丙烷、雙(甲苯磺醯氧基)丁烷、p-硝基苄基甲苯磺酸酯、o-硝基苄基甲苯磺酸酯、1,2,3-伸苯基三(甲基磺酸酯)、p-甲苯磺酸吡啶鎓鹽、p-甲苯磺酸嗎啉鎓鹽、p-甲苯磺酸乙酯、p-甲苯磺酸丙酯、p-甲苯磺酸丁酯、p-甲苯磺酸異丁酯、p-甲苯磺酸甲酯、p-甲苯磺酸苯乙酯、氰基甲基p-甲苯磺酸酯、2,2,2-三氟乙基p-甲苯磺酸酯、2-羥丁基p-甲苯磺酸酯、N-乙基-4-甲苯碸醯胺以外，又例如以下之式(5)至式(9)、式(14)至式(49)所示之化合物等。a compound which generates an acid via heat, for example, bis(toluenesulfonyloxy)ethane, bis(toluenesulfonyloxy)propane, bis(toluenesulfonyloxy)butane, p-nitrobenzyltoluenesulfonate Acid ester, o-nitrobenzyl tosylate, 1,2,3-phenylphenyl tris(methylsulfonate), pyridinium p-toluenesulfonate, morpholinium p-toluenesulfonate , p-toluenesulfonate ethyl ester, propyl p-toluenesulfonate, butyl p-toluenesulfonate, isobutyl p-toluenesulfonate, methyl p-toluenesulfonate, phenylethyl p-toluenesulfonate , cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, N-ethyl-4-toluene Other than the guanamine, for example, a compound represented by the following formulas (5) to (9), and formula (14) to formula (49).

[化4][Chemical 4]

[化5][Chemical 5]

[化6][Chemical 6]

[化7][Chemistry 7]

[化8][化8]

本實施形態之樹脂組成物中，(D)成分之含量，相對於(A)成分與(B)成分之合計量100質量份，較佳為0.01至5質量份。未達0.01質量份時，將造成熱硬化性降低而使得耐溶劑性不佳以外，也會有降低感受光照射之感度的情形。又，超過5質量份時，也會有降低組成物之保存安定性的情形。In the resin composition of the present embodiment, the content of the component (D) is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the total of the components (A) and (B). When it is less than 0.01 part by mass, the thermosetting property is lowered to make the solvent resistance poor, and the sensitivity of the perceived light irradiation may be lowered. Moreover, when it exceeds 5 mass parts, the storage stability of a composition may fall.

＜(E)成分＞<(E) component>

本實施形態中，也可含有(E)成分之增感劑。該(E)成分，就促進本實施形態之熱硬化膜形成後之光二聚化反應等觀點為有效者。In the present embodiment, a sensitizer of the component (E) may be contained. The component (E) is effective in promoting the photodimerization reaction after the formation of the thermosetting film of the present embodiment.

(E)成分之增感劑，例如二苯甲酮、蒽、蒽醌、噻噸酮及其衍生物以及硝基苯基化合物等。其中又以二苯甲酮衍生物及硝基苯基化合物為特佳。具體而言，例如N,N-二乙基胺基二苯甲酮、2-硝基茀、2-硝基茀酮、5-硝基苊萘、9-羥基甲基蒽、4-硝基桂皮酸或4-硝基聯苯基等。特別是以二苯甲酮衍生物之N,N-二乙基胺基二苯甲酮為佳。此外，增感劑並不限定於上述內容。又，增感劑可單獨使用或將2種以上之化合物組合使用亦可。A sensitizer of the component (E), such as benzophenone, anthraquinone, anthracene, thioxanthone and a derivative thereof, and a nitrophenyl compound. Among them, benzophenone derivatives and nitrophenyl compounds are particularly preferred. Specifically, for example, N,N-diethylaminobenzophenone, 2-nitroguanidine, 2-nitrofluorenone, 5-nitroguanidine, 9-hydroxymethylhydrazine, 4-nitro Cinnamic acid or 4-nitrobiphenyl. In particular, N,N-diethylaminobenzophenone of the benzophenone derivative is preferred. Further, the sensitizer is not limited to the above. Further, the sensitizer may be used singly or in combination of two or more kinds of compounds.

本實施形態中，(E)成分之增感劑的使用比例，相對於(A)成分之100質量份，以0.1至20質量份為佳，更佳為0.2至10質量份。該比例遠低於0.1質量份時，將會有無法充分得到作為增感劑之效果的情形。又，大於20質量份時，將會有造成透過率降低及塗膜龜裂之情形。In the present embodiment, the use ratio of the sensitizer of the component (E) is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, per 100 parts by mass of the component (A). When the ratio is much less than 0.1 part by mass, there is a case where the effect as a sensitizer cannot be sufficiently obtained. Further, when it is more than 20 parts by mass, there is a case where the transmittance is lowered and the coating film is cracked.

＜溶劑＞<solvent>

本實施形態之樹脂組成物為以溶解於溶劑所得之溶液狀態使用。所使用之溶劑，為溶解(A)成分(B)成分，及(C)成分所得者。又，必要時含有(D)成分或(E)成分之情形，亦為將其溶解所得之溶夜，又，含有後述其他添加劑之情形時，亦為將其溶解所得之溶夜。只要具有溶解能力之溶劑時，其則種類及結構等並未有特別限定條件。具體而言，例如(A)成分或(B)成分聚合時所使用之溶劑等。該些溶劑，可單獨使用1種，或將2種以上組合使用。The resin composition of the present embodiment is used in the form of a solution obtained by dissolving in a solvent. The solvent to be used is obtained by dissolving the component (B) and the component (C). Further, when the component (D) or the component (E) is contained as necessary, it is also a nighttime solution obtained by dissolving the same, and when it contains other additives described later, it is also a dissolved night obtained by dissolving it. When there is a solvent having a dissolving power, the type, structure, and the like are not particularly limited. Specifically, for example, a solvent used in the polymerization of the component (A) or the component (B), and the like. These solvents may be used alone or in combination of two or more.

＜其他添加劑＞<Other additives>

此外，本實施形態之樹脂組成物，於無損本發明之效果之情形，必要時可再添加、含有矽烷偶合劑、界面活性劑、流動調整劑、顏料、染料、保存安定劑、消泡劑及抗氧化劑等其他之添加劑。Further, in the case where the effect of the present invention is not impaired, the resin composition of the present embodiment may further contain, if necessary, a decane coupling agent, a surfactant, a flow regulator, a pigment, a dye, a storage stabilizer, an antifoaming agent, and Other additives such as antioxidants.

＜樹脂組成物＞<Resin composition>

本實施形態之樹脂組成物為含有(A)成分之具有光二聚化部位及熱交聯部位之丙烯酸共聚物、(B)之聚醯亞胺前驅物、(C)成分之交聯劑，並配合所期望，可再含有(D)成分之酸或熱酸發生劑、(E)成分之增感劑，此外，可再含有其他添加劑中所選出之1種以上之添加劑。又，樹脂組成物通常為使用溶解於該些溶劑所得之溶液。The resin composition of the present embodiment is a crosslinking agent containing the (2) component, the acrylic copolymer having a photodimerization site and a thermal crosslinking site, the polyimine precursor of (B), and the component (C). Further, it may further contain an acid or thermal acid generator of the component (D) and a sensitizer of the component (E), and may further contain one or more additives selected from other additives. Further, the resin composition is usually a solution obtained by dissolving in the solvents.

樹脂組成物中，(A)成分與(B)成分之組成比，以質量份比為5：95至60：40為佳。(A)成分之含量大幅低於該組成比時，會有產生配向不良之疑慮。又，(A)成分之含量大幅高於該組成比時，除雙折射率降低以外，塗膜也有白濁化之疑慮。In the resin composition, the composition ratio of the component (A) to the component (B) is preferably 5:95 to 60:40 by mass. When the content of the component (A) is significantly lower than the composition ratio, there is a concern that alignment failure occurs. Further, when the content of the component (A) is significantly higher than the composition ratio, in addition to the decrease in the birefringence, the coating film is also cloudy.

又，(A)成分之羥價通常為1至3mmol/g，(B)成分之酸價通常為2至4mmol/g，於上述範圍之中，(A)成分與(B)成分之組成比為5：95至40：60之範圍內之情形，可使上層之配向成分流動而提高配向感度，進而得到高雙折射率。Further, the hydroxyl value of the component (A) is usually from 1 to 3 mmol/g, and the acid value of the component (B) is usually from 2 to 4 mmol/g, and in the above range, the composition ratio of the component (A) to the component (B) In the case of the range of 5:95 to 40:60, the alignment component of the upper layer can be made to increase the alignment sensitivity, thereby obtaining a high birefringence.

其中，(A)成分之羥價係指，(A)成分1g中所含之游離羥基被乙醯化時，為中和乙酸所需要之氫氧化鈣的mmol數。又，(B)成分之酸價，係指為中和(B)成分1g中所含游離的酸基所需要之氫氧化鈣的mmol數。Here, the hydroxyl value of the component (A) means the number of mmoles of calcium hydroxide required for neutralizing acetic acid when the free hydroxyl group contained in 1 g of the component (A) is acetonitrile. Further, the acid value of the component (B) means the number of mmoles of calcium hydroxide required to neutralize the free acid group contained in 1 g of the component (B).

本實施形態之樹脂組成物的較佳例示，係如以下所示。Preferred examples of the resin composition of the present embodiment are as follows.

[1]：(A)成分與(B)成分之合計量100質量份為基準，為含有10至100質量份之(C)成分樹脂組成物。[1] The resin composition of the component (C) is contained in an amount of 10 to 100 parts by mass based on 100 parts by mass of the total of the components (A) and (B).

[2]：(A)成分與(B)成分之合計量100質量份為基準，含有10至100質量份之(C)成分，及溶劑的樹脂組成物。[2] A resin composition containing 10 to 100 parts by mass of the component (C) and a solvent, based on 100 parts by mass of the total of the component (A) and the component (B).

[3]：(A)成分與(B)成分之合計量100質量份為基準，為含有10至100質量份之(C)成分、0.01至5質量份之(D)成分，及溶劑的樹脂組成物。[3]: a resin containing 10 to 100 parts by mass of the component (C), 0.01 to 5 parts by mass of the component (D), and a solvent, based on 100 parts by mass of the total of the components (A) and (B). Composition.

本實施形態之樹脂組成物作為溶液使用之情形，其組成比例或製造方法等詳述如以下內容。In the case where the resin composition of the present embodiment is used as a solution, the composition ratio, the production method, and the like are described in detail below.

本實施形態之樹脂組成物中，固體成分之比例，只要使各成分均勻地溶解於溶劑之範圍，並未有特別限定之內容，一般之固體成分比例為1至80質量%。其中，較佳為3至60質量%，更佳為5至40質量%。其中，固體成分係指由溶劑中去除樹脂組成物之全成分後所得之成分。In the resin composition of the present embodiment, the ratio of the solid component is not particularly limited as long as the components are uniformly dissolved in the solvent, and the solid content ratio is usually from 1 to 80% by mass. Among them, it is preferably from 3 to 60% by mass, more preferably from 5 to 40% by mass. Here, the solid content means a component obtained by removing the entire component of the resin composition from a solvent.

本實施形態之樹脂組成物之製造方法，並未有特別限定。例如，將(A)成分溶解於溶劑，再於該溶液中，使(B)成分，再加入(C)成分及(D)成分依特定比例混合，形成均勻溶液之方法等。又，於該製造方法之適當階段中，可配合其必要性再添加其他添加劑，進行混合之方法等。The method for producing the resin composition of the present embodiment is not particularly limited. For example, a method in which the component (A) is dissolved in a solvent, and the component (B) is further added to the component (C) and the component (D) is mixed in a specific ratio to form a homogeneous solution. Further, in an appropriate stage of the production method, a method of mixing other additives, mixing, and the like may be added in accordance with the necessity.

本實施形態之樹脂組成物之製造中，溶劑中經聚合反應所得之丙烯酸聚合物之溶液可無加工處理下使用。該情形，係於(A)成分之溶液中，與前述內容相同般，加入(B)成分、(C)成分及(D)成分等而形成均勻之溶液。此時，於調整濃度等目的時，可再追加溶劑亦可。其中，丙烯酸聚合物生成過程中所使用之溶劑，與樹脂組成物之製造時為調整濃度等所使用之溶劑，可為相同之溶劑亦可，或由不同之適當溶劑中分別選擇使用。In the production of the resin composition of the present embodiment, the solution of the acrylic polymer obtained by the polymerization reaction in the solvent can be used without processing. In this case, in the solution of the component (A), the components (B), (C) and (D) are added in the same manner as described above to form a homogeneous solution. At this time, when adjusting the concentration or the like, a solvent may be added. The solvent used in the production of the acrylic polymer and the solvent used for adjusting the concentration during the production of the resin composition may be the same solvent or may be selected from different suitable solvents.

依以上方法所製得之本實施形態之樹脂組成物的溶液。其以使用孔徑0.2μm左右之過濾器過濾以後予以使用為佳。A solution of the resin composition of the present embodiment obtained by the above method. It is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

＜塗膜、硬化膜及液晶配向層＞<Coating film, cured film, and liquid crystal alignment layer>

使用本實施形態之樹脂組成物，依以下之方法形成塗膜。Using the resin composition of the present embodiment, a coating film was formed by the following method.

首先，於基板上，使用迴轉塗佈、流動塗佈、滾筒塗佈、縫隙塗佈、縫隙之後進行迴轉塗佈、塗料噴射塗佈或印刷等方法，塗佈樹脂組成物。隨後，於熱壓板或烘箱等進行預乾燥(預燒焙)結果，即可形成塗膜。其後，對此塗膜經由加熱處理(後燒焙)結果，即可形成硬化膜。First, a resin composition is applied onto the substrate by a method such as spin coating, flow coating, roll coating, slit coating, slit, spin coating, paint spray coating, or printing. Subsequently, the film is formed by pre-drying (pre-baking) on a hot platen or an oven or the like. Thereafter, the cured film is formed by heat treatment (post-baking) of the coating film.

塗佈樹脂組成物之基板，例如可使用矽/二氧化矽被覆基板、氮化矽基板、玻璃基板、石英基板或ITO基板等。又，例如亦可使用被覆鋁、鉬或鉻等金屬之基板。此外，例如，三乙醯纖維素薄膜、聚酯薄膜及丙烯酸薄膜等樹脂薄膜等作為基板使用。As the substrate on which the resin composition is applied, for example, a ruthenium/ruthenium dioxide-coated substrate, a tantalum nitride substrate, a glass substrate, a quartz substrate, an ITO substrate, or the like can be used. Further, for example, a substrate coated with a metal such as aluminum, molybdenum or chromium may be used. Further, for example, a resin film such as a triacetyl cellulose film, a polyester film, or an acrylic film is used as a substrate.

塗膜之預燒焙之條件，例如，可採用由溫度70至160℃、時間0.3至60分鐘之範圍中適當選擇之加熱溫度及加熱時間。加熱溫度及加熱時間，較佳為80至140℃、0，5至10分鐘。The pre-baking conditions of the coating film, for example, a heating temperature and a heating time which are appropriately selected from the range of temperature 70 to 160 ° C and time 0.3 to 60 minutes can be employed. The heating temperature and the heating time are preferably 80 to 140 ° C for 0, 5 to 10 minutes.

塗膜之後燒焙條件，一般為採用由溫度140至250℃之範圍中配合加熱方法等所適當選擇之加熱溫度。又，加熱時間亦為同樣，例如，於熱壓板上之情形為5至30分鐘，於烘箱中之情形為為30至90分鐘等。The baking condition after the film coating is generally a heating temperature appropriately selected by a heating method such as a temperature in the range of 140 to 250 °C. Further, the heating time is also the same, for example, 5 to 30 minutes on the hot platen, 30 to 90 minutes in the oven, and the like.

以上述條件為基礎，經由使本實施形態之樹脂組成物硬化結果，即可將濾光膜(CF)等所造成之基板之高低段差充分地覆蓋，而得到平坦化效果，同時亦可形成具有高透明性之硬化膜。又，硬化膜之膜厚度，例如可為0.1至30μm，其可考慮所使用之基板的段差或光學、電學性質等作適當之選擇。By the curing of the resin composition of the present embodiment, the retardation of the substrate caused by the filter film (CF) or the like can be sufficiently covered by the above-mentioned conditions to obtain a flattening effect and can also be formed. Highly transparent cured film. Further, the film thickness of the cured film may be, for example, 0.1 to 30 μm, which may be appropriately selected in consideration of the step difference or optical and electrical properties of the substrate to be used.

依上述方法所得之硬化膜，為可進行偏光照射之液晶配向材料，即，具有可使具有液晶性之化合物形成配向之液晶配向層的機能。此時，偏光照射所使用之偏光光線，以偏光UV(ultraviolet)為佳。偏光UV，通常為使用150至450nm波長之紫外光。隨後，以垂直或斜射方向對於室溫或加熱狀態下之硬化膜照射直線偏光。The cured film obtained by the above method is a liquid crystal alignment material which can be subjected to polarized light irradiation, that is, a function of a liquid crystal alignment layer which can form a liquid crystal compound. At this time, the polarized light used for the polarized light irradiation is preferably UV (ultraviolet). Polarized UV, usually using ultraviolet light with a wavelength of 150 to 450 nm. Subsequently, the hardened film at room temperature or in a heated state is irradiated with linear polarization in a vertical or oblique direction.

於依以上方法由本實施形態之樹脂組成物所形成之液晶配向層之上，塗佈相位差材料之後，加熱至液晶相轉移溫度，使相位差材料形成液晶狀態後，進行光硬化。如此，可於液晶配向層上形成具有光學異向性之層，即形成相位差材料。經由該方法於液晶晶元內部配置相位差材料之構成內容，與於液晶晶元之外部配置相位差材料之以往的構成內容相比較時，得知其可提高液晶晶元之反差比。The phase difference material is applied onto the liquid crystal alignment layer formed of the resin composition of the present embodiment by the above method, and then heated to a liquid crystal phase transition temperature to form a liquid crystal state of the phase difference material, followed by photocuring. Thus, a layer having optical anisotropy can be formed on the liquid crystal alignment layer, that is, a phase difference material can be formed. The content of the phase difference material disposed in the liquid crystal cell by this method is compared with the conventional configuration in which the phase difference material is disposed outside the liquid crystal cell, and it is found that the contrast ratio of the liquid crystal cell can be improved.

相位差材料，例如，可使用具有聚合性基之液晶單體，或含有其之組成物等。形成有液晶配向層之基板為薄膜之情形，其適合作為光學異向性薄膜。該些相位差材料，為具有水平配向、膽固醇配向、垂直配向、混合配向、二軸配向等配向性之材料，其可分別配合所需要之相位差使用。As the phase difference material, for example, a liquid crystal monomer having a polymerizable group, a composition containing the same, or the like can be used. In the case where the substrate on which the liquid crystal alignment layer is formed is a film, it is suitable as an optical anisotropic film. The phase difference materials are materials having an alignment property such as horizontal alignment, cholesterol alignment, vertical alignment, mixed alignment, and biaxial alignment, which can be used in combination with a desired phase difference.

又，可將具有依上述方式所形成之液晶配向層的2片基板，介由調距器使液晶配向層相互對向之方式貼合，其後，於該些基板之間，經由注入液晶，而可作為形成液晶配向之液晶顯示元件。Moreover, the two substrates having the liquid crystal alignment layer formed as described above can be bonded to each other via the distance adjuster so that the liquid crystal alignment layers face each other, and then the liquid crystal is injected between the substrates. It can be used as a liquid crystal display element for forming a liquid crystal alignment.

如此，本實施形態之樹脂組成物，適合使用於構成各種光學異向性薄膜或液晶顯示元件。As described above, the resin composition of the present embodiment is suitably used for constituting various optical anisotropic films or liquid crystal display elements.

又，本實施形態之樹脂組成物適合作為形成薄膜電晶體(TFT)型液晶顯示元件及有機EL元件等各種顯示器之保護膜、平坦膜、絕緣膜等硬化膜之材料。特別是除濾光膜(CF)之保護膜材料(CF保護膜材料)以外，亦適合作為可形成TFT型液晶元件之層間絕緣膜，或有機EL元件之絕緣膜等的材料。In addition, the resin composition of the present embodiment is suitable as a material for forming a cured film such as a protective film, a flat film, or an insulating film of various displays such as a thin film transistor (TFT) liquid crystal display device and an organic EL device. In addition to the protective film material (CF protective film material) of the filter film (CF), it is suitable as a material which can form an interlayer insulating film of a TFT type liquid crystal element, or an insulating film of an organic EL element.

本實施形態之樹脂組成物作為CF保護膜材料使用之情形，所得之CF保護膜，除可覆蓋濾光膜之段差，使其平坦化以外，亦具有液晶配向材料之機能。因此，亦可作為具有配向性之CF保護膜使用。When the resin composition of the present embodiment is used as a CF protective film material, the obtained CF protective film has a function of a liquid crystal alignment material in addition to the step of covering the filter film to flatten it. Therefore, it can also be used as an CF protective film having an alignment property.

圖1為本實施形態之液晶晶元模式的構成圖。該圖中，液晶層108為挾夾於2片的基板101、111之間。基板111上，為形成ITO110與配向膜109。又，基板101上，為依序形成濾光膜102，與CF保護膜103，與相位差材料105，與ITO106，與配向膜107。該情形中，CF保護膜103為具有配向膜之機能，故可不需使用對應於圖2之配向膜204的膜。Fig. 1 is a view showing the configuration of a liquid crystal cell mode in the embodiment. In the figure, the liquid crystal layer 108 is sandwiched between two substrates 101 and 111. On the substrate 111, an ITO 110 and an alignment film 109 are formed. Further, on the substrate 101, a filter film 102, a CF protective film 103, a phase difference material 105, an ITO 106, and an alignment film 107 are sequentially formed. In this case, since the CF protective film 103 functions as an alignment film, it is not necessary to use a film corresponding to the alignment film 204 of Fig. 2 .

[實施例][Examples]

以下，將列舉實施例，對本發明作更詳細之說明，但本發明並不受該些實施例所限定。Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited by the examples.

[實施例所使用之簡稱][Abbreviation used in the examples]

以下實施例所使用之簡稱，係具有以下之意義。The abbreviations used in the following examples have the following meanings.

＜丙烯酸聚合物＞<acrylic polymer>

HEMA：2-羥甲基丙烯酸乙酯HEMA: 2-hydroxyethyl methacrylate

CIN：4-(6-甲基丙烯氧己基-1-氧基)桂皮酸甲酯CIN: methyl 4-(6-methylpropoxyhexyl-1-oxy) cinnamate

AIBN：α、α’-偶氮二異丁腈AIBN: α, α'-azobisisobutyronitrile

＜聚醯亞胺前驅物＞<Polyimide precursor>

BPDA：3,3’,4,4’-聯苯基四羧酸二酐BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

ODPA：4,4’-氧代二苯二甲酸酐ODPA: 4,4'-oxophthalic anhydride

CBDA：1,2,3,4-環丁烷四羧酸二酐CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

TFMB：2,2’-三氟甲基-4,4’-二胺基聯苯基TFMB: 2,2'-trifluoromethyl-4,4'-diaminobiphenyl

＜交聯劑＞<crosslinker>

CYM：賽麥爾303(三井科技製)CYM: Saimer 303 (Mitsui Technology)

＜酸或熱酸發生劑＞<Acid or thermal acid generator>

PTSA：p-甲苯磺酸1水和物PTSA: p-toluenesulfonic acid 1 water and substance

＜溶劑＞<solvent>

CHN：環己酮CHN: cyclohexanone

NMP：N-甲基吡咯啶酮NMP: N-methylpyrrolidone

依以下之合成例所製得之丙烯酸共聚物之數平均分子量及重量平均分子量為使用日本分光(股)製GPC裝置(Shodex(登記商標)管柱KF803L及KF804L)，使溶出之溶劑四氫呋喃於管柱中(管柱溫度40℃)以流量1ml/分鐘流動進行溶離之條件下所測定之值。又，下述之數平均分子量(以下，亦稱為Mn)及重量平均分子量(以下，亦稱為Mw)，為以聚苯乙烯換算值表示。The number average molecular weight and the weight average molecular weight of the acrylic copolymer obtained by the following synthesis examples were obtained by using a GPC apparatus (Shodex (registered trademark) column KF803L and KF804L) manufactured by JASCO Corporation, and the solvent tetrahydrofuran was dissolved in the tube. The value measured under the conditions in which the column (column temperature: 40 ° C) was flow-dissolved at a flow rate of 1 ml/min. Further, the following average molecular weight (hereinafter also referred to as Mn) and weight average molecular weight (hereinafter also referred to as Mw) are expressed in terms of polystyrene.

又，聚醯亞胺前驅物之Mn及Mw，為使用Shodex公司製GPC裝置(Shodex(登記商標)管柱KD803及KD805)，溶出溶劑N,N,-二甲基甲醯胺(添加劑為，溴化鋰-水和物(LiBr‧H2O)為30mmol/L、磷酸‧無水結晶(o-磷酸)為30mmol/L、四氫呋喃為10ml/L)，於管柱中(管柱溫度50℃)以流量1ml/分鐘流動進行溶離之條件下所測定者。又，下述Mn及Mw為，聚乙二醇、聚氧化乙烯換算值表示。Further, the Mn and Mw of the polyimide precursor are a GPC apparatus (Shodex (registered trademark) column KD803 and KD805) manufactured by Shodex Co., Ltd., and the solvent N, N,-dimethylformamide (additive, Lithium bromide-water (LiBr‧H 2 O) is 30 mmol/L, phosphoric acid ‧ anhydrous crystals (o-phosphoric acid is 30 mmol/L, tetrahydrofuran is 10 ml/L), in a column (column temperature 50 ° C) The flow rate was measured at a flow rate of 1 ml/min for dissolution. Further, the following Mn and Mw are represented by polyethylene glycol and polyethylene oxide equivalent values.

＜合成例1＞<Synthesis Example 1>

使CIN 42.0g、HEMA 18.0g、AIBN 1.3g溶解於CHN 166.8g之中，於80℃下反應20小時而製得丙烯酸聚合物溶液(所得固體成分濃度為27質量%)(P1)。所得之丙烯酸聚合物之Mn為8,500、Mw為16,500。42.0 g of CIN, 18.0 g of HEMA, and 1.3 g of AIBN were dissolved in 166.8 g of CHN, and reacted at 80 ° C for 20 hours to obtain an acrylic polymer solution (the obtained solid content concentration was 27% by mass) (P1). The obtained acrylic polymer had an Mn of 8,500 and a Mw of 16,500.

＜合成例2＞<Synthesis Example 2>

使TFMB 16.0g溶解於NMP 114.1g中。隨後，加入BPDA 12.5g，於40℃下反應20小時而製得聚醯亞胺前驅物溶液(所得固體成分濃度為20質量%)(P2)。所得之聚醯亞胺前驅物之Mn為12,600、Mw為27,500。16.0 g of TFMB was dissolved in 114.1 g of NMP. Subsequently, 12.5 g of BPDA was added, and the reaction was carried out at 40 ° C for 20 hours to obtain a polyimide precursor solution (the obtained solid content concentration was 20% by mass) (P2). The obtained polyimine precursor had an Mn of 12,600 and a Mw of 27,500.

＜合成例3＞<Synthesis Example 3>

使TFMB 5.1g溶解於NMP 72.2g中。隨後，加入ODPA 4.7g，於室溫下反應20小時而製得聚醯亞胺前驅物溶液(所得固體成分濃度為12質量%)(P3)。所得之聚醯亞胺前驅物之Mn為7,000、Mw為15,800。5.1 g of TFMB was dissolved in NMP 72.2 g. Subsequently, 4.7 g of ODPA was added, and the mixture was reacted at room temperature for 20 hours to obtain a polyimide precursor solution (the obtained solid content concentration was 12% by mass) (P3). The obtained polyimide intermediate precursor had an Mn of 7,000 and a Mw of 15,800.

＜合成例4＞<Synthesis Example 4>

使TFMB 233.8g溶解於NMP 2111.6g中。隨後，加入CBDA 142.9g，於室溫下反應20小時而製得聚醯亞胺前驅物溶液(所得固體成分濃度為15質量%)(P4)。所得之聚醯亞胺前驅物之Mn為12,400、Mw為43,000。233.8 g of TFMB was dissolved in NMP 2111.6 g. Subsequently, 142.9 g of CBDA was added, and the mixture was reacted at room temperature for 20 hours to obtain a polyimide precursor solution (the obtained solid content concentration was 15% by mass) (P4). The obtained polyimine precursor had an Mn of 12,400 and a Mw of 43,000.

＜實施例1至實施例3及比較例1至比較例4＞<Example 1 to Example 3 and Comparative Example 1 to Comparative Example 4>

依表3所示組成內容，分別製造實施例1至實施例3及比較例1至比較例4之各組成物，並分別評估其耐溶劑性、透過率、配向性以及雙折射率。Each of the compositions of Examples 1 to 3 and Comparative Examples 1 to 4 was produced according to the composition shown in Table 3, and the solvent resistance, transmittance, alignment, and birefringence were evaluated, respectively.

[耐溶劑性之評估][Evaluation of Solvent Resistance]

將實施例1至實施例3及比較例1至比較例4之各組成物，使用旋轉塗佈器塗佈於矽晶圓上之後，於熱壓板上以溫度80℃進行120秒鐘之預燒焙。隨後，將此塗膜於熱風循環式烘箱中以溫度230℃進行30分鐘之後燒焙，形成膜厚2.0μm之硬化膜。膜厚為使用VEECO公司製DEKTAK150進行測定。Each of the compositions of Examples 1 to 3 and Comparative Examples 1 to 4 was applied onto a ruthenium wafer using a spin coater, and then preheated on a hot plate at a temperature of 80 ° C for 120 seconds. Baked. Subsequently, this coating film was baked in a hot air circulating oven at a temperature of 230 ° C for 30 minutes, and then baked to form a cured film having a film thickness of 2.0 μm. The film thickness was measured using DEKTAK150 manufactured by VEECO.

其次，將此硬化膜浸漬於CHN或NMP中60秒鐘之後，分別於溫度100℃下乾燥60秒鐘，隨後測定其膜厚。浸漬CHN或NMP後之膜厚未產生變化者為○、觀察出浸漬後膜厚減少者為「×」。Next, the cured film was immersed in CHN or NMP for 60 seconds, and then dried at a temperature of 100 ° C for 60 seconds, respectively, and then the film thickness was measured. The film thickness after immersion of CHN or NMP was not changed, and the film thickness after immersion was observed to be "x".

[光透過率(透明性)之評估][Evaluation of light transmittance (transparency)]

將實施例1至實施例3及比較例1至比較例4之各組成物，使用旋轉塗佈器塗佈於石英基板上之後，於熱壓板上，以溫度80℃、120秒鐘進行預燒焙。隨後，將此塗膜於熱風循環式烘箱中，進行溫度230℃、30分鐘之後燒焙，形成膜厚2.0μm之硬化膜。膜厚為使用VEECO公司製DEKTAK150進行測定。Each of the compositions of Examples 1 to 3 and Comparative Examples 1 to 4 was applied onto a quartz substrate using a spin coater, and then preliminarily heated on a hot plate at a temperature of 80 ° C for 120 seconds. Baked. Subsequently, the coating film was baked in a hot air circulating oven, and baked at a temperature of 230 ° C for 30 minutes to form a cured film having a film thickness of 2.0 μm. The film thickness was measured using DEKTAK150 manufactured by VEECO.

其次，此硬化膜為使用紫外線可見分光光度計((股)島津製作所製SHIMADZU UV-2550(型號))，測定波長400nm時之透過率。Next, the cured film was measured by using an ultraviolet-visible spectrophotometer (SHIMADZU UV-2550 (model) manufactured by Shimadzu Corporation), and the transmittance at a wavelength of 400 nm was measured.

[配向感度之評估][Evaluation of alignment sensitivity]

將實施例1至實施例3及比較例1至比較例4之各組成物使用旋轉塗佈器塗佈於ITO基板上之後，於熱壓板上以溫度80℃、120秒鐘時間進行預燒焙。隨後，將此塗膜於熱風循環式烘箱中以溫度230℃、30分之條件進行後燒焙，形成膜厚2.0μm之硬化膜。膜厚為使用VEECO公司製DEKTAK150進行測定。Each of the compositions of Examples 1 to 3 and Comparative Examples 1 to 4 was applied onto an ITO substrate using a spin coater, and then calcined on a hot plate at a temperature of 80 ° C for 120 seconds. Baked. Subsequently, this coating film was baked in a hot air circulating oven at a temperature of 230 ° C for 30 minutes, and then baked to form a cured film having a film thickness of 2.0 μm. The film thickness was measured using DEKTAK150 manufactured by VEECO.

其次，將偏光UV之波長313nm的直線偏光，以相對於ITO基板上之硬化膜為垂直之方向下進行照射。隨後，將由液晶單體所形成之相位差材料溶液使用旋轉塗佈器塗佈於此基板上，隨後，於熱壓板上進行80℃、60秒鐘之預燒焙，形成膜厚1.4μm之塗膜。其次，於氮雰圍下，對此基板上之塗膜，以1,000mJ/cm2之UV光進行曝光，使相位差材料硬化。將依此方式製得之基板挾夾於偏光板，確認該硬化之相位差材料的相位差狀態，求取為使硬化膜形成配向性之必要的偏光UV之曝光量作為配向感度。又，即使使用3,000mJ/cm2之UV光曝光下，也不會顯示配向性者則以「×」表示。Next, the linear light having a polarization wavelength of 313 nm was polarized and irradiated in a direction perpendicular to the cured film on the ITO substrate. Subsequently, the phase difference material solution formed of the liquid crystal monomer is coated on the substrate using a spin coater, and then pre-baked at 80 ° C for 60 seconds on a hot plate to form a film thickness of 1.4 μm. Coating film. Next, the coating film on the substrate was exposed to UV light of 1,000 mJ/cm 2 in a nitrogen atmosphere to cure the phase difference material. The substrate 制 obtained in this manner was sandwiched between the polarizing plates, and the phase difference state of the hardened phase difference material was confirmed, and the exposure amount of the polarized light UV necessary for forming the cured film to obtain the alignment property was determined as the alignment sensitivity. Further, even if exposure is performed using UV light of 3,000 mJ/cm 2 , the alignment is not indicated by "x".

[雙折射率之評估][Evaluation of birefringence]

將實施例1至實施例3及比較例1至比較例4之各組成物使用旋轉塗佈器塗佈於石英基板上之後，於熱壓板上進行溫度80℃、120秒鐘之預燒焙。隨後，將此塗膜於熱風循環式烘箱中，以溫度230℃、30分鐘之條件進行後燒焙，形成膜厚2.0μm之硬化膜。膜厚度為使用VEECO公司製DEKTAK150進行測定。Each of the compositions of Examples 1 to 3 and Comparative Examples 1 to 4 was applied onto a quartz substrate using a spin coater, and then pre-baked at a temperature of 80 ° C for 120 seconds on a hot platen. . Subsequently, this coating film was baked in a hot air circulating oven at a temperature of 230 ° C for 30 minutes, and then baked to form a cured film having a film thickness of 2.0 μm. The film thickness was measured using DEKTAK150 manufactured by VEECO.

此硬化膜，為使用相位差薄膜測定裝置(AXOMETRICS Inc.製Axo Scan)，測定波長590nm時之雙折射率。This cured film was measured for a birefringence at a wavelength of 590 nm using a retardation film measuring apparatus (Axo Scan manufactured by AXOMETRICS Inc.).

[評估結果][evaluation result]

進行以上評估所得之結果係如表4所示。The results of the above evaluation are shown in Table 4.

實施例1至實施例3之組成物所形成之硬化膜，顯示出高配向感度。因此，得知實施例1至實施例3之組成物，可形成有效率之液晶配向材料。此外，亦確認其具有高度透明性，且對於CHN及NMP之任一者接具有耐性。又，亦顯示高雙折射率。The cured films formed from the compositions of Examples 1 to 3 exhibited high alignment sensitivity. Therefore, the compositions of Examples 1 to 3 were known to form an efficient liquid crystal alignment material. In addition, it is also confirmed to have high transparency and to be resistant to any of CHN and NMP. Also, high birefringence is also exhibited.

又，比較例1之組成物所形成之硬化膜，其雙折射率及耐溶劑性皆較低，為得到其配向性，必須具有相對於實施例1至實施例3之情形為300倍之曝光量。又，比較例2至比較例4之組成物所形成之硬化膜，雖可具有高雙折射率與耐溶劑性，但其未顯示出配向性。Further, the cured film formed of the composition of Comparative Example 1 had low birefringence and solvent resistance, and in order to obtain the alignment property, it was necessary to have an exposure of 300 times with respect to the cases of Examples 1 to 3. the amount. Further, the cured films formed of the compositions of Comparative Examples 2 to 4 had high birefringence and solvent resistance, but did not exhibit alignment.

如以上所述般，得知本發明之樹脂組成物所得之硬化膜，確實具有高雙折射率，且具有優良之光透過性、耐溶劑性及配向性。因此，本發明之樹脂組成物可提供使用於具有上述各種優良特性之硬化膜，即，可提供使用於液晶配向材料，此外，亦可形成相位差材料。As described above, the cured film obtained by the resin composition of the present invention has a high birefringence and excellent light transmittance, solvent resistance and alignment. Therefore, the resin composition of the present invention can provide a cured film which is used for various excellent properties as described above, that is, it can be used for a liquid crystal alignment material, and a phase difference material can also be formed.

[產業上之利用性][Industrial use]

本發明之樹脂組成物，極適合作為光學異向性薄膜或液晶顯示元件之液晶配向材料，此外，於薄膜電晶體(TFT)型液晶顯示元件或有機EL元件等各種顯示器中，亦極適合作為形成保護膜、平坦膜及絕緣膜等硬化膜之材料，特別是適合作為形成TFT型液晶元件之層間絕緣膜、濾光膜之保護膜或有機EL元件之絕緣膜等的材料。The resin composition of the present invention is excellent as a liquid crystal alignment material for an optically anisotropic film or a liquid crystal display element, and is also suitable as a liquid crystal display element or an organic EL element in various displays such as a thin film transistor (TFT) type liquid crystal display element. A material for forming a cured film such as a protective film, a flat film, or an insulating film is particularly suitable as a material for forming an interlayer insulating film of a TFT-type liquid crystal element, a protective film of a filter film, or an insulating film of an organic EL element.

101．．．基板101. . . Substrate

102．．．濾光膜102. . . Filter film

103．．．CF保護膜103. . . CF protective film

105．．．相位差材料105. . . Phase difference material

106．．．ITO106. . . ITO

107．．．配向膜107. . . Orientation film

108．．．液晶層108. . . Liquid crystal layer

109．．．配向膜109. . . Orientation film

110．．．ITO110. . . ITO

111．．．基板111. . . Substrate

202．．．濾光膜202. . . Filter film

204．．．配向膜204. . . Orientation film

205．．．相位差材料205. . . Phase difference material

[圖1]依本實施形態所得之液晶晶元之結構模式圖。Fig. 1 is a structural schematic view showing a liquid crystal cell obtained in the present embodiment.

[圖2]以往液晶晶元之結構模式圖。Fig. 2 is a structural schematic view of a conventional liquid crystal cell.

101．．．基板101. . . Substrate

102．．．濾光膜102. . . Filter film

103．．．CF保護膜103. . . CF protective film

105．．．相位差材料105. . . Phase difference material

106．．．ITO106. . . ITO

107．．．配向膜107. . . Orientation film

108．．．液晶層108. . . Liquid crystal layer

109．．．配向膜109. . . Orientation film

110．．．ITO110. . . ITO

111．．．基板111. . . Substrate

Claims (16)

一種樹脂組成物，其特徵為含有，(A)具有由疏水性基所形成之光二聚化部位與由親水性基所形成之熱交聯部位之丙烯酸共聚物，與(B)主鏈具有聯苯基結構之聚醯亞胺前驅物，與(C)使該(A)成分與該(B)成分形成交聯之交聯劑。 A resin composition comprising (A) an acrylic copolymer having a photodimerization site formed by a hydrophobic group and a thermal crosslinking site formed by a hydrophilic group, and having a (B) main chain a polyphenylenimine precursor of a phenyl structure, and (C) a crosslinking agent which crosslinks the component (A) with the component (B). 如申請專利範圍第1項之樹脂組成物，其中，前述(A)成分為，含有具有光二聚化部位之單體，與具有熱交聯部位之單體的單體混合物經聚合反應所得之丙烯酸共聚物。 The resin composition of claim 1, wherein the component (A) is an acrylic acid obtained by polymerizing a monomer mixture having a photodimerization site and a monomer having a thermal crosslinking site. Copolymer. 如申請專利範圍第2項之樹脂組成物，其中，前述(A)成分相對於全單體混合物之合計量，為含有25莫耳%至90莫耳%之由具有光二聚化部位之單體的單體混合物經聚合反應所得之丙烯酸共聚物。 The resin composition of claim 2, wherein the component (A) is a monomer having a photodimerization site in an amount of from 25 mol% to 90 mol% based on the total amount of the total monomer mixture. The acrylic copolymer obtained by polymerization of the monomer mixture. 如申請專利範圍第1項之樹脂組成物，其中，前述(A)成分之光二聚化部位為桂皮醯基。 The resin composition of claim 1, wherein the photodimerization site of the component (A) is cinnabarinyl. 如申請專利範圍第1項之樹脂組成物，其中，前述(A)成分之熱交聯部位為羥基或羧基。 The resin composition of claim 1, wherein the thermally crosslinked portion of the component (A) is a hydroxyl group or a carboxyl group. 如申請專利範圍第1項之樹脂組成物，其中，前述(B)成分為含有由四羧酸二酐與二胺化合物經共聚合反應所得之結構單位的聚醯亞胺前驅物，該四羧酸二酐及該二胺化合物之至少一者為具有聯苯基結構者。 The resin composition of claim 1, wherein the component (B) is a polyimine precursor containing a structural unit obtained by copolymerization of a tetracarboxylic dianhydride and a diamine compound, the tetracarboxylic acid At least one of the acid dianhydride and the diamine compound is a compound having a biphenyl structure. 如申請專利範圍第6項之樹脂組成物，其中，前 述四羧酸二酐為聯苯基四羧酸二酐。 For example, the resin composition of claim 6 of the patent scope, wherein The tetracarboxylic dianhydride is biphenyltetracarboxylic dianhydride. 如申請專利範圍第6項之樹脂組成物，其中，前述(B)成分為前述結構單位具有三氟甲基之聚醯亞胺前驅物。 The resin composition of claim 6, wherein the component (B) is a polyimine precursor having a trifluoromethyl group as the structural unit. 如申請專利範圍第1項之樹脂組成物，其中，前述(B)成分之聚醯亞胺前驅物為主鏈具有脂環結構者。 The resin composition of claim 1, wherein the polyimine precursor of the component (B) has an alicyclic structure as a main chain. 如申請專利範圍第9項之樹脂組成物，其中，前述(B)成分為含有由四羧酸二酐與二胺化合物經共聚合反應所得之結構單位的聚醯亞胺前驅物，且該四羧酸二酐及該二胺化合物之至少一者為具有脂環結構者。 The resin composition of claim 9, wherein the component (B) is a polyimine precursor containing a structural unit obtained by copolymerization of a tetracarboxylic dianhydride and a diamine compound, and the fourth At least one of the carboxylic acid dianhydride and the diamine compound is one having an alicyclic structure. 如申請專利範圍第1項之樹脂組成物，其中，前述(C)成分之交聯劑為具有羥甲基或烷氧基羥甲基之交聯劑。 The resin composition of claim 1, wherein the crosslinking agent of the component (C) is a crosslinking agent having a methylol group or an alkoxymethylol group. 如申請專利範圍第1項之樹脂組成物，其中，依前述(A)成分與前述(B)成分之合計量100質量份為基準，為含有10至100質量份之前述(C)成分。 The resin composition of the first aspect of the invention, wherein the component (C) is contained in an amount of 10 to 100 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B). 如申請專利範圍第1項之樹脂組成物，其尚含有(D)成分之酸或熱酸發生劑。 The resin composition of claim 1 which further contains the acid or thermal acid generator of the component (D). 如申請專利範圍第13項之樹脂組成物，其中，依前述(A)成分與前述(B)成分之合計量100質量份為基準，為含有0.1至10質量份之前述(D)成分。 The resin composition of claim 13 which contains 0.1 to 10 parts by mass of the component (D) based on 100 parts by mass of the total of the component (A) and the component (B). 一種液晶配向材料，其特徵為，使用申請專利範圍第1~14項中任一項之樹脂組成物所得者。 A liquid crystal alignment material obtained by using the resin composition of any one of claims 1 to 14. 一種相位差材料，其特徵為，使用申請專利範圍 第1~14項中任一項之樹脂組成物所得之硬化膜而形成者。A phase difference material characterized by the use of a patent application The cured film obtained from the resin composition of any one of items 1 to 14 is formed.
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KR101791446B1 (en) * 2009-07-21 2017-10-30 닛산 가가쿠 고교 가부시키 가이샤 Composition forming heat cured film having photo alignment property

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