TWI613223B - Resin composition, liquid crystal alignment material and phase difference material - Google Patents
Resin composition, liquid crystal alignment material and phase difference material Download PDFInfo
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Description
本發明關於樹脂組成物、液晶配向材料及位相差材料。 The present invention relates to a resin composition, a liquid crystal alignment material, and a phase difference material.
一般地,於液晶顯示元件、有機EL(電致發光)元件及固體攝像元件等的光裝置中,為了保護元件表面,防止來自於製程的溶劑或熱,而設置保護膜。對於此保護膜,不僅要求耐溶劑性或耐熱性,而且亦要求與所保護的基板之密接性高、透明性高。 In general, in an optical device such as a liquid crystal display device, an organic EL (electroluminescence) device, or a solid-state imaging device, a protective film is provided to protect the surface of the device from solvent or heat from the process. The protective film is required to have not only solvent resistance or heat resistance but also high adhesion to the substrate to be protected and high transparency.
上述保護膜例如係作為彩色液晶顯示裝置或固體攝像元件中所用的彩色濾光片之保護膜使用。此時,為了將基底的彩色濾光片或黑色矩陣平坦化,例如要求可以1μm以上的膜厚來形成保護膜。特別地,於製造STN方式或TFT方式的彩色液晶顯示元件時,由於必須非常嚴密地進行彩色濾光片基板與對向基板的貼合,使基板間的晶胞間隙成為均勻者係必要而不可欠缺,在保護膜亦要求對基底 的高平坦化能力。再者,為了維持穿透彩色濾光片的光之透過率,在保護膜亦需要高的透明性。 The protective film is used, for example, as a protective film for a color filter used in a color liquid crystal display device or a solid-state image sensor. At this time, in order to planarize the color filter or the black matrix of the substrate, for example, it is required to form a protective film with a film thickness of 1 μm or more. In particular, when manufacturing a color liquid crystal display device of an STN type or a TFT type, it is necessary to closely bond the color filter substrate and the counter substrate, and it is necessary to make the cell gap between the substrates uniform. Missing, the protective film is also required to be on the substrate High flattening ability. Furthermore, in order to maintain the transmittance of light penetrating through the color filter, high transparency is also required in the protective film.
近年來,檢討藉由在液晶顯示器的晶胞內導入位相差材料,而謀求低成本化及輕量化。 In recent years, it has been reviewed to introduce a phase difference material into a cell of a liquid crystal display to reduce cost and weight.
圖2係藉由習知技術形成有液晶配向膜的液晶胞200之示意構成圖。於此圖中,液晶層208係被夾持在2片基板201、211之間。於基板211上形成有ITO210與配向膜209。又,於基板201上,依順序形成有彩色濾光片202、彩色濾光片(CF)的罩面層(以下稱為CF罩面層)203、配向膜204、位相差材料205、ITO206與配向膜207。 Fig. 2 is a schematic view showing a liquid crystal cell 200 in which a liquid crystal alignment film is formed by a conventional technique. In the figure, the liquid crystal layer 208 is sandwiched between the two substrates 201, 211. An ITO 210 and an alignment film 209 are formed on the substrate 211. Further, on the substrate 201, a color filter 202, a color filter (CF) overcoat layer (hereinafter referred to as a CF overcoat layer) 203, an alignment film 204, a phase difference material 205, and an ITO 206 are sequentially formed. Alignment film 207.
於以往的液晶胞中,為了在硬化前使上述位相差材料形成用的聚合性液晶配向,必須在其下層另外設置可使液晶配向的膜,即配向膜。配向膜係經由摩擦處理或偏光照射等的步驟來形成。即,如圖2所示,以往一般係在CF罩面層203上形成配向膜204後,在其上形成由液晶單體等的聚合性液晶所得之位相差材料205。即,形成彩色濾光片202後,更必須層合CF罩面層203與配向膜204這兩層來形成,製程係複雜者。 In the conventional liquid crystal cell, in order to align the polymerizable liquid crystal for forming the phase difference material before the curing, it is necessary to separately provide a film which can align the liquid crystal, that is, an alignment film. The alignment film is formed through a step such as rubbing treatment or polarized light irradiation. In other words, as shown in FIG. 2, a phase difference material 205 obtained by forming a polymer film of a liquid crystal monomer or the like is formed on the CF overcoat layer 203. That is, after the color filter 202 is formed, it is necessary to form the CF overcoat layer 203 and the alignment film 204 in two layers, and the process is complicated.
因此,強烈希望同時滿足複數不同的要求特性之膜與形成其的材料之提供。具體地,要求兼任配向膜與CF罩面層之膜、與形成此膜的材料。藉此,在液晶顯示器的製造上,可享受低成本化、製程數的削減、產量的提高等之很大的優點。 Therefore, it is strongly desired to simultaneously satisfy the provision of a plurality of different desired characteristics of the film and the material from which it is formed. Specifically, it is required to serve both the film of the alignment film and the CF overcoat layer and the material for forming the film. As a result, in the manufacture of a liquid crystal display, it is possible to enjoy the advantages of low cost, reduction in the number of processes, and improvement in throughput.
一般地,於CF罩面層中,使用透明性高的丙烯酸樹脂。於此等丙烯酸樹脂中,從處理性及塗佈性的觀點來看,廣泛使用丙二醇單甲基醚或丙二醇單甲基乙基乙酸酯等的二醇系溶劑、乳酸乙酯或乳酸丁酯等的酯系溶劑、環己酮或甲基戊基酮等的酮系溶劑。而且,藉由熱或光使丙烯酸樹脂硬化,而展現耐熱性或耐溶劑性(例如參照專利文獻1或2)。 Generally, an acrylic resin having high transparency is used in the CF overcoat layer. Among these acrylic resins, a glycol solvent such as propylene glycol monomethyl ether or propylene glycol monomethyl ethyl acetate, ethyl lactate or butyl lactate is widely used from the viewpoint of handleability and coatability. A ketone solvent such as an ester solvent such as cyclohexanone or methyl amyl ketone. Further, the acrylic resin is cured by heat or light to exhibit heat resistance or solvent resistance (for example, refer to Patent Document 1 or 2).
然而,根據本發明者們的檢討,於由以往的熱硬化性或光硬化性的丙烯酸樹脂所構成的CF罩面層中,雖然得到透明性或平坦化性,但清楚瞭解即使對其施予摩擦處理,也無法展現充分的液晶配向性。因此,可知無法將以往的CF罩面層直接適用於上述兼任配向膜與CF罩面層的膜。 However, according to the review by the present inventors, in the CF overcoat layer composed of the conventional thermosetting or photocurable acrylic resin, although transparency or flatness is obtained, it is clear that even if it is administered Friction treatment does not exhibit sufficient liquid crystal alignment. Therefore, it can be seen that the conventional CF overcoat layer cannot be directly applied to the above-mentioned film which is also an alignment film and a CF overcoat layer.
另一方面,作為配向膜,以往係使用由溶劑可溶性聚醯亞胺或聚醯胺酸所成的材料。有報告說此等材料係藉由後烘烤時使完全醯亞胺化而得到耐溶劑性,同時藉由摩擦處理亦可展現充分的配向性(參照專利文獻3)。然而,視為CF罩面層時,由於厚膜化而有透明性大幅降低的問題。又,聚醯亞胺或聚醯胺酸雖然可溶於N-甲基吡咯啶酮或γ-丁內酯等的溶劑中,但由於在二醇系的溶劑或酯系的溶劑中之溶解性低,而亦有難以適用於CF罩面層的生產線之問題。 On the other hand, as the alignment film, a material made of a solvent-soluble polyimine or a polyamic acid has conventionally been used. It has been reported that these materials are completely imidized by post-baking to obtain solvent resistance, and at the same time, sufficient alignment property can be exhibited by rubbing treatment (see Patent Document 3). However, when it is regarded as a CF overcoat layer, there is a problem that transparency is largely lowered due to thick film formation. Further, although polyimine or polylysine is soluble in a solvent such as N-methylpyrrolidone or γ-butyrolactone, solubility in a solvent of a glycol type or an ester type solvent It is low, but there are also problems in the production line that is difficult to apply to the CF overcoat.
[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]特開2005-037920號公報 [Patent Document 3] JP-A-2005-037920
本發明係以上述知識或檢討結果為基礎而完成者。即,本發明之目的係在於提供一種樹脂組成物,其具有優異的配向性、耐溶劑性、耐熱性及透明性,可形成適用作為CF罩面層的硬化膜。 The present invention has been completed on the basis of the above knowledge or review results. That is, an object of the present invention is to provide a resin composition which has excellent alignment property, solvent resistance, heat resistance and transparency, and can form a cured film which is suitable as a CF overcoat layer.
本發明的其它目的及優點係可由以下的記載所明知。 Other objects and advantages of the present invention will be made clear from the description below.
本發明的第1態樣係關於一種樹脂組成物,其特徵為含有在側鏈具有環己烯環的聚合物(A成分)。 A first aspect of the invention relates to a resin composition comprising a polymer (component A) having a cyclohexene ring in a side chain.
於本發明的第1態樣中,A成分的聚合物之主鏈較佳為具有不飽和雙鍵的單體之聚合物。 In the first aspect of the invention, the main chain of the polymer of the component A is preferably a polymer of a monomer having an unsaturated double bond.
於本發明的第1態樣中,A成分的聚合物之主鏈較佳為丙烯酸聚合物。 In the first aspect of the invention, the main chain of the polymer of the component A is preferably an acrylic polymer.
於本發明的第1態樣中,A成分的聚合物較佳為由聚乙烯醇所衍生。 In the first aspect of the invention, the polymer of the component A is preferably derived from polyvinyl alcohol.
於本發明的第1態樣中,A成分的聚合物之主鏈較佳為含有環構造。 In the first aspect of the invention, the main chain of the polymer of the component A preferably has a ring structure.
於本發明的第1態樣中,A成分的聚合物之主鏈較佳 為聚酯樹脂。 In the first aspect of the invention, the main chain of the polymer of the component A is preferably It is a polyester resin.
於本發明的第1態樣中,A成分的聚合物之主鏈較佳為酚醛清漆樹脂。 In the first aspect of the invention, the main chain of the polymer of the component A is preferably a novolak resin.
於本發明的第1態樣中,A成分的聚合物較佳為環烯烴聚合物。 In the first aspect of the invention, the polymer of the component A is preferably a cycloolefin polymer.
於本發明的第1態樣中,A成分的聚合物較佳為具有成為交聯基的側鏈。 In the first aspect of the invention, the polymer of the component A preferably has a side chain which becomes a crosslinking group.
於本發明的第1態樣中,A成分的聚合物所具有的交聯基較佳為選自由羥基、羧基、環氧基及丙烯醯基所成之群中的至少1個官能基。 In the first aspect of the invention, the crosslinking group of the polymer of the component A is preferably at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group and an acryl group.
於本發明的第1態樣中,較佳為更含有因熱而反應的交聯劑(C成分)。 In the first aspect of the invention, it is preferred to further contain a crosslinking agent (component C) which reacts with heat.
於本發明的第1態樣中,較佳為更含有交聯觸媒(E成分)。 In the first aspect of the invention, it is preferred to further contain a crosslinking catalyst (component E).
本發明的第2態樣係關於一種樹脂組成物,其含有式(1)所示的在末端具有環己烯環的化合物(B成分)與黏結劑聚合物(D成分),
於本發明的第2態樣中,(D)成分較佳為含有式(2)所示的構造單位之聚酯樹脂,
於本發明的第2態樣中,(D)成分較佳為丙烯酸聚合物。 In the second aspect of the invention, the component (D) is preferably an acrylic polymer.
於本發明的第2態樣中,較佳為更含有因熱而反應的交聯劑(C成分)。 In the second aspect of the invention, it is preferred to further contain a crosslinking agent (component C) which reacts with heat.
於本發明的第2態樣中,較佳更含有交聯觸媒(E成分)。 In the second aspect of the invention, it is preferred to further contain a crosslinking catalyst (component E).
本發明的第3態樣係關於一種液晶配向材料,其特徵為使用本發明的第1及第2態樣之樹脂組成物而得。 A third aspect of the invention relates to a liquid crystal alignment material which is obtained by using the resin compositions of the first and second aspects of the invention.
本發明的第4態樣係關於一種位相差材料,其特徵為使用由本發明的第1及第2態樣之樹脂組成物而得之硬化 膜來形成。 A fourth aspect of the present invention relates to a phase difference material characterized by using the resin composition of the first and second aspects of the present invention. The film is formed.
依照本發明的第1態樣之樹脂組成物,係具有優異的配向性、耐溶劑性、耐熱性及透明性,可形成適用作為CF罩面層的硬化膜。 The resin composition according to the first aspect of the present invention has excellent alignment properties, solvent resistance, heat resistance and transparency, and can form a cured film which is suitable as a CF overcoat layer.
依照本發明的第2態樣之樹脂組成物,係具有優異的配向性、耐溶劑性、耐熱性及透明性,可形成適用作為CF罩面層的硬化膜。 The resin composition according to the second aspect of the present invention has excellent alignment properties, solvent resistance, heat resistance and transparency, and can form a cured film which is suitable as a CF overcoat layer.
本發明的第3態樣之液晶配向材料,係透光性、耐熱性、耐溶劑性及配向性優異。 The liquid crystal alignment material according to the third aspect of the present invention is excellent in light transmittance, heat resistance, solvent resistance, and alignment.
本發明的第4態樣之位相差材料,係可配置於液晶胞內。使用此位相差材料的液晶胞係可提高對比。 The phase difference material of the fourth aspect of the present invention can be disposed in the liquid crystal cell. The use of this phase difference material of the liquid crystal cell line can improve the contrast.
100、200‧‧‧液晶胞 100,200‧‧‧ liquid crystal cell
101、111、201、211‧‧‧基板 101, 111, 201, 211‧‧‧ substrates
102、202‧‧‧彩色濾光片 102, 202‧‧‧ color filters
103、203‧‧‧CF罩面層 103, 203‧‧‧CF overcoat
105、205‧‧‧位相差材料 105, 205‧‧‧ phase difference materials
106、110、206、210‧‧‧ITO 106, 110, 206, 210‧‧‧ ITO
107、109、204、207、209‧‧‧配向膜 107, 109, 204, 207, 209‧‧ ‧ alignment film
108、208‧‧‧液晶層 108, 208‧‧‧ liquid crystal layer
圖1係本發明的實施形態之液晶胞的示意構成圖。 Fig. 1 is a schematic configuration diagram of a liquid crystal cell according to an embodiment of the present invention.
圖2係以往的液晶胞之示意構成圖。 Fig. 2 is a schematic configuration diagram of a conventional liquid crystal cell.
本發明關於樹脂組成物、使用此樹脂組成物而形成的液晶配向材料、及使用由此樹脂組成物所得之硬化膜而形成的位相差材料。更詳細地,關於具有優異的配向性、耐溶劑性、耐熱性及透明性,可形成適用作為CF罩面層的 硬化膜之樹脂組成物、使用此樹脂組成物而形成的液晶配向材料、及使用此液晶配向材料而形成的位相差材料。由本發明的樹脂組成物所形成之硬化膜,係適合作為亦具備液晶顯示器中的CF罩面層之機能的膜,而且由於具備對用於形成位相差層的聚合性液晶之配向機能,故亦適合於內藏位相差層的形成。 The present invention relates to a resin composition, a liquid crystal alignment material formed using the resin composition, and a phase difference material formed using the cured film obtained from the resin composition. In more detail, with respect to having excellent alignment, solvent resistance, heat resistance and transparency, it can be suitably used as a CF overcoat layer. A resin composition of a cured film, a liquid crystal alignment material formed using the resin composition, and a phase difference material formed using the liquid crystal alignment material. The cured film formed of the resin composition of the present invention is suitable as a film which also functions as a CF overcoat layer in a liquid crystal display, and also has an alignment function for a polymerizable liquid crystal for forming a phase difference layer. It is suitable for the formation of phase difference layers in the built-in phase.
即,依照本發明的樹脂組成物,例如可以1μm以上的膜厚塗佈,可形成一種可能硬化膜,其除了高透明性、高耐溶劑性,還具有液晶配向能力。因此,此樹脂組成物係可用作為液晶配向膜或平坦化膜的形成材料。特別地,可將以往獨立形成的液晶配向膜與彩色濾光片之罩面層,當作兼具兩者的特性之液晶配向層(CF罩面層)」設置在液晶胞的中。因此,可實現製程的簡略化及製程數減低所致的低成本化等。 That is, the resin composition according to the present invention can be applied, for example, at a film thickness of 1 μm or more, and can form a possible cured film which has liquid crystal alignment ability in addition to high transparency and high solvent resistance. Therefore, this resin composition can be used as a material for forming a liquid crystal alignment film or a planarization film. In particular, a liquid crystal alignment film (CF overcoat layer) having both characteristics of the liquid crystal alignment film and the color filter which have been independently formed in the past can be provided in the liquid crystal cell. Therefore, the simplification of the process and the cost reduction due to the reduction in the number of processes can be achieved.
再者,本發明的樹脂組成物,由於可溶於二醇系的溶劑及乳酸酯系的溶劑中,故適合於使用以此等溶劑為主的平坦化膜之製作生產線。 In addition, since the resin composition of the present invention is soluble in a glycol-based solvent and a lactic acid ester-based solvent, it is suitable for use in a production line for using a planarizing film mainly composed of such a solvent.
以下,對於本發明的樹脂組成物、液晶配向材料及位相差材料,邊舉出具體例邊詳細說明。 Hereinafter, the resin composition, the liquid crystal alignment material, and the phase difference material of the present invention will be described in detail with reference to specific examples.
本發明的實施形態之樹脂組成物中所可含有的成分係如以下。 The components which can be contained in the resin composition of the embodiment of the present invention are as follows.
(A)成分:在側鏈具有環己烯環的聚合物 (A) component: a polymer having a cyclohexene ring in its side chain
(B)成分:在末端具有環己烯環的化合物 (B) component: a compound having a cyclohexene ring at the terminal
(C)成分:交聯劑 (C) Component: Crosslinker
(D)成分:其它聚合物(本說明書中亦稱為黏結劑聚合物) (D) Ingredients: Other polymers (also referred to as binder polymers in this specification)
(E)成分:交聯觸媒 (E) component: cross-linking catalyst
又,於本發明的實施形態之樹脂組成物中,較佳的成分組合係如以下。 Further, in the resin composition of the embodiment of the present invention, preferred component combinations are as follows.
[1]:以(A)成分的100質量份為基礎,含有1至100質量份的(C)成分之樹脂組成物。 [1]: A resin composition containing 1 to 100 parts by mass of the component (C) based on 100 parts by mass of the component (A).
[2]:以(B)成分與(D)成分的合計量100質量份為基礎,含有1至100質量份的(C)成分之樹脂組成物。 [2]: The resin composition of the component (C) is contained in an amount of 1 to 100 parts by mass based on 100 parts by mass of the total of the components (B) and (D).
[3]:以(A)成分的100質量份為基礎,含1至100質量份的(C)成分及溶劑之樹脂組成物。 [3]: a resin composition containing 1 to 100 parts by mass of the component (C) and a solvent based on 100 parts by mass of the component (A).
[4]:以(B)成分與(D)成分的合計量100質量份為基礎,含有1至100質量份的(C)成分及溶劑之樹脂組成物。 [4]: A resin composition containing 1 to 100 parts by mass of the component (C) and a solvent, based on 100 parts by mass of the total of the components (B) and (D).
[5]:以(A)成分的100質量份為基礎,含有1至100質量份的(C)成分、0.01至5質量份的(E)成分及溶劑之樹脂組成物。 [5]: A resin composition containing 1 to 100 parts by mass of the component (C), 0.01 to 5 parts by mass of the component (E), and a solvent, based on 100 parts by mass of the component (A).
[6]:以(B)成分與(D)成分的合計量100質量份為基礎,含有1至100質量份的(C)成分、0.01至5質量份的(E)成分及溶劑之樹脂組成物。 [6]: Based on 100 parts by mass of the total of the components (B) and (D), the resin composition contains 1 to 100 parts by mass of the component (C), 0.01 to 5 parts by mass of the component (E), and a solvent. Things.
以下詳細說明構成本發明的樹脂組成物之各成分的詳細。 The details of each component constituting the resin composition of the present invention will be described in detail below.
(A)成分 (A) component
本發明的實施形態之樹脂組成物中所含有的(A)成 分,係在側鏈具有環己烯環的聚合物。聚合物主鏈的骨架等係沒有特別的限定。此聚合物較佳為具有因熱而自反應或與交聯劑進行交聯的反應性基。 (A) which is contained in the resin composition of the embodiment of the present invention A polymer having a cyclohexene ring in a side chain. The skeleton of the polymer main chain or the like is not particularly limited. The polymer preferably has a reactive group which is self-reacted by heat or crosslinked with a crosslinking agent.
作為(A)成分的聚合物之例,可舉出丙烯酸聚合物、乙烯基聚合物、聚酯樹脂、酚醛清漆樹脂及環烯烴聚合物等。 Examples of the polymer of the component (A) include an acrylic polymer, a vinyl polymer, a polyester resin, a novolak resin, and a cycloolefin polymer.
作為在聚合物導入環己烯環的方法,可舉出在具有環氧基的聚合物附加環己烯羧酸之方法,使具有羥基的聚合物與環己烯二羧酸酐進行縮合反應之方法,使具有羥基或胺基的聚合物與環己烯羧醯氯反應之方法,及使用具有環己烯環的單體進行聚合之方法等。 As a method of introducing a cyclohexene ring into a polymer, a method of adding a cyclohexene carboxylic acid to a polymer having an epoxy group, and a method of condensing a polymer having a hydroxyl group with cyclohexene dicarboxylic anhydride A method of reacting a polymer having a hydroxyl group or an amine group with cyclohexene carboxyfluorene chloride, a method of polymerizing using a monomer having a cyclohexene ring, and the like.
以下顯示(A)成分的聚合物之具體例。 Specific examples of the polymer of the component (A) are shown below.
上述式(A-1)至(A-7)中,X1表示氫原子或羧基,Y1表示氫原子或甲基,R1表示氫原子、烷基或乙醯基,R2表示氫原子或環氧丙基。又,n與m的比例為n/m=100/0至30/70。式(A-7)中,A1表示脂環式基、由脂環式基與脂肪 族基所成的基或含有苯環構造的基,B1表示脂環式基、由脂環式基與脂肪族基所成的基或含有苯環構造的基。 In the above formulae (A-1) to (A-7), X 1 represents a hydrogen atom or a carboxyl group, Y 1 represents a hydrogen atom or a methyl group, R 1 represents a hydrogen atom, an alkyl group or an ethyl fluorenyl group, and R 2 represents a hydrogen atom. Or epoxy propyl. Further, the ratio of n to m is n/m = 100/0 to 30/70. In the formula (A-7), A 1 represents an alicyclic group, a group derived from an alicyclic group and an aliphatic group, or a group having a benzene ring structure, and B 1 represents an alicyclic group and an alicyclic group. a group formed with an aliphatic group or a group having a benzene ring structure.
(A)成分的重量平均分子量,以聚苯乙烯換算較佳為1,000至50,000。 The weight average molecular weight of the component (A) is preferably from 1,000 to 50,000 in terms of polystyrene.
說明丙烯酸系的(A)成分之合成方法。 A method for synthesizing the acrylic (A) component will be described.
得到如上述具有環己烯環的丙烯酸聚合物之方法係沒有特別的限定,例如預先藉由自由基聚合等,生成具有環氧丙基或羥基的丙烯酸聚合物,其次使此與環己烯羧酸、環己烯羧醯氯或環己烯二羧酸酐等反應,而成為(A)成分的丙烯酸聚合物。 The method for obtaining an acrylic polymer having a cyclohexene ring as described above is not particularly limited, and for example, an acrylic polymer having a glycidyl group or a hydroxyl group is formed by radical polymerization or the like in advance, and this is followed by a cyclohexene carboxyl group. An acrylic polymer which is reacted with an acid, cyclohexene carboxy fluorene chloride or cyclohexene dicarboxylic anhydride to form (A).
作為具有環氧丙基的自由基聚合性單體,例如可舉出甲基丙烯酸環氧丙酯、丙烯酸環氧丙酯、丙烯酸4-羥丁酯環氧丙基醚及甲基丙烯酸4-羥丁酯環氧丙基醚等。 Examples of the radically polymerizable monomer having a glycidyl group include glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl acrylate epoxypropyl ether, and 4-hydroxy methacrylate. Butyl ester epoxypropyl ether and the like.
作為具有羥基的自由基聚合性單體,例如可舉出羥基苯乙烯、N-(羥基苯基)丙烯醯胺、N-(羥基苯基)甲基丙烯醯胺、N-(羥基苯基)馬來醯亞胺、丙烯酸2-羥乙酯、丙烯酸2-羥丙酯、5-丙烯醯氧基-6-羥基降冰片烯-2-羧酸-6-內酯、甲基丙烯酸2-羥乙酯、甲基丙烯酸2-羥丙酯及5-甲基丙烯醯氧基-6-羥基降冰片烯-2-羧酸-6-內酯等。 Examples of the radical polymerizable monomer having a hydroxyl group include hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, and N-(hydroxyphenyl). Maleimide, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-propenyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, 2-hydroxy methacrylate Ethyl ester, 2-hydroxypropyl methacrylate and 5-methylpropenyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone.
於本發明的實施形態之樹脂組成物中,在得到具有有效於環氧丙基或羥基等的環己烯環之導入的特定官能基之丙烯酸聚合物時,可併用能與具有特定官能基的單體共聚合之單體。以下舉出該單體的具體例,惟不受此等所限定。 In the resin composition of the embodiment of the present invention, when an acrylic polymer having a specific functional group which is effective for introduction of a cyclohexene ring such as a glycidyl group or a hydroxyl group is obtained, a combination of a specific functional group and a specific functional group can be obtained. Monomer copolymerized monomer. Specific examples of the monomer are given below, but are not limited thereto.
作為能與具有特定官能基的單體共聚合之單體,例如可舉出丙烯酸酯化合物、甲基丙烯酸酯化合物、馬來醯亞胺化合物、丙烯腈、馬來酸酐、苯乙烯化合物及乙烯基化合物等。 Examples of the monomer copolymerizable with a monomer having a specific functional group include an acrylate compound, a methacrylate compound, a maleimide compound, acrylonitrile, maleic anhydride, a styrene compound, and a vinyl group. Compounds, etc.
作為上述單體的具體例,可舉出丙烯酸、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)甲基丙烯醯胺、N-(羧基苯基)丙烯醯胺、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、甲基丙烯酸蒽酯、丙烯酸苯酯、丙烯酸2,2,2-三氟乙酯、丙烯酸第三丁酯、丙烯酸環己酯、丙烯酸異冰片酯、丙烯酸2-甲氧基乙酯、甲氧基三乙二醇丙烯酸酯、丙烯酸2-乙氧基乙酯、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、丙烯酸8-乙基-8-三環癸酯、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、甲基丙烯酸蒽基甲酯、甲基丙烯酸苯酯、甲基丙烯酸2,2,2-三氟乙酯、甲基丙烯酸第三丁酯、甲基丙烯酸環己酯、甲基丙烯酸異冰片酯、甲基丙烯酸2-甲氧基乙酯、甲氧基三乙二醇甲基丙烯酸酯、甲基丙烯酸2-乙氧基乙酯、甲基丙烯酸四氫糠酯、甲基丙烯酸3-甲氧基丁酯、甲基丙烯酸2-甲基-2-金剛烷酯、γ-丁內酯甲基丙烯酸酯、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、乙烯基醚、甲基乙烯基醚、苄基乙烯基醚、乙烯基萘、乙烯基蒽、乙烯基咔唑、2-羥乙基乙烯基醚、苯基乙烯基醚及丙基乙烯基醚、苯乙烯、甲基苯乙烯、氯苯乙烯、溴苯乙烯、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。 Specific examples of the monomer include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloxy)ethyl)phthalate, and mono-(2-(methacryloxime). Oxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)propenamide, acrylic acid Methyl ester, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, decyl acrylate, decyl methacrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, third butyl acrylate Ester, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxy triethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methyl acrylate Oxybutyl butyl ester, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-acrylic acid Tricyclononyl ester, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, decyl methacrylate, methacrylic acid methacrylate Ester, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methyl methacrylate Oxyethyl ester, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, methacrylic acid 2-methyl-2-adamantyl ester, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate and 8-ethyl-8-tricyclodecyl methacrylate, vinyl ether, methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, Vinyl hydrazine, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether and propyl vinyl ether, styrene, methyl styrene, chlorostyrene, bromostyrene, malayan Amine, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like.
得到本發明的實施形態之樹脂組成物中所用之具有環己烯環的丙烯酸聚合物之方法係沒有特別的限定,例如使具有特定官能基的單體、其以外之可共聚合的單體及依所欲之聚合引發劑等在共存的溶劑中,於50至110℃的溫度下聚合反應而得。當時所用的溶劑,只要是溶解作為構成具有特定官能基的丙烯酸聚合物之單體、與具有特定官能基的丙烯酸聚合物者,則沒有特別的限定。作為具體例,可舉出後述的溶劑。 The method of obtaining the cyclohexene ring-containing acrylic polymer used in the resin composition of the embodiment of the present invention is not particularly limited, and examples thereof include a monomer having a specific functional group, and a copolymerizable monomer other than The polymerization initiator or the like is obtained by a polymerization reaction at a temperature of 50 to 110 ° C in a solvent which is coexistent. The solvent to be used at the time is not particularly limited as long as it is a monomer which dissolves an acrylic polymer having a specific functional group and an acrylic polymer having a specific functional group. As a specific example, the solvent mentioned later is mentioned.
如此所得之具有特定官能基的丙烯酸聚合物,通常係溶解在溶劑中的溶液之狀態。 The acrylic polymer having a specific functional group thus obtained is usually in a state of a solution dissolved in a solvent.
其次,使所得之具有特定官能基的丙烯酸聚合物與具有環己烯環的化合物反應,可得到(A)成分之具有環己烯環的丙烯酸聚合物(以下亦稱為特定共聚物)。此時,通常使用具有特定官能基的丙烯酸聚合物之溶液。具體地,例如有以下所示的合成方法等。 Next, an acrylic polymer having a specific functional group obtained is reacted with a compound having a cyclohexene ring to obtain a cyclohexene ring-containing acrylic polymer (hereinafter also referred to as a specific copolymer) of the component (A). At this time, a solution of an acrylic polymer having a specific functional group is usually used. Specifically, for example, there are synthesis methods and the like shown below.
使具有環氧丙基的丙烯酸聚合物之溶液與環己烯羧酸,在氯化苄基三乙銨等的觸媒之存在下,於80℃至150℃的溫度進行反應,可得到特定共聚物。此時,所用的溶 劑,只要是溶解構成特定共聚物的單體與特定共聚物者,則沒有特別的限定。作為具體例,可舉出後述的溶劑。 The specific copolymerization can be obtained by reacting a solution of a propylene group-containing acrylic polymer with cyclohexene carboxylic acid in the presence of a catalyst such as benzyltriethylammonium chloride at a temperature of from 80 ° C to 150 ° C. Things. At this time, the solution used The agent is not particularly limited as long as it dissolves the monomer constituting the specific copolymer and the specific copolymer. As a specific example, the solvent mentioned later is mentioned.
使具有羥基的丙烯酸聚合物之溶液與環己烯二羧酸酐,在氯化苄基三乙銨等的觸媒之存在下,於80℃至150℃的溫度進行反應,可得到特定共聚物。此時,所用的溶劑是溶解構成特定共聚物的單體與特定共聚物者,較佳為不具有羥基的溶劑。 A specific copolymer is obtained by reacting a solution of a hydroxyl group-containing acrylic polymer with cyclohexene dicarboxylic anhydride in the presence of a catalyst such as benzyltriethylammonium chloride at a temperature of from 80 ° C to 150 ° C. In this case, the solvent to be used is a solvent which dissolves a monomer constituting a specific copolymer and a specific copolymer, and preferably a solvent which does not have a hydroxyl group.
使具有羥基的丙烯酸聚合物之溶液與環己烯二羧醯氯,在三乙胺等的三級胺之存在下,於0℃至40℃的溫度進行反應後,去除所生成的鹽及胺,可得到特定共聚物。 此時,所用的溶劑是溶解構成特定共聚物的單體與特定共聚物者,較佳為不具有羥基的溶劑。 The solution of the acrylic polymer having a hydroxyl group is reacted with cyclohexene dicarboxyfluorene chloride in the presence of a tertiary amine such as triethylamine at a temperature of from 0 ° C to 40 ° C to remove the formed salt and amine. , a specific copolymer can be obtained. In this case, the solvent to be used is a solvent which dissolves a monomer constituting a specific copolymer and a specific copolymer, and preferably a solvent which does not have a hydroxyl group.
如以上所得之特定共聚物,通常為在溶劑中溶解有特定共聚物的溶液之狀態。 The specific copolymer obtained as above is usually in the form of a solution in which a specific copolymer is dissolved in a solvent.
又,將如上述所得之特定共聚物的溶液投入攪拌下的二乙基醚或水等中,以使再沈澱,過濾‧洗淨所生成的沈澱物後,於常壓或減壓下,藉由常溫或加熱乾燥,可成為特定共聚物的粉體。藉由如此的操作,可去除與特定共聚物共存的聚合引發劑或未反應單體,結果得到經精製的特定共聚物之粉體。再者,於一次的操作無法充分精製時,可將所得之粉體再溶解於溶劑中,重複進行上述的操作。 Further, a solution of the specific copolymer obtained as described above is placed in diethyl ether or water under stirring to reprecipitate, and the resulting precipitate is washed and washed, and then taken under normal pressure or reduced pressure. It can be a powder of a specific copolymer by drying at room temperature or by heating. By such an operation, the polymerization initiator or the unreacted monomer which coexists with the specific copolymer can be removed, and as a result, the powder of the purified specific copolymer can be obtained. Further, when the primary operation cannot be sufficiently purified, the obtained powder can be redissolved in a solvent, and the above operation can be repeated.
於本發明的實施形態之樹脂組成物中,可直接使用特定共聚物的粉體,或者也可使該粉體例如再溶解於後述的溶劑中,作為溶液的狀態使用。 In the resin composition of the embodiment of the present invention, the powder of the specific copolymer may be used as it is, or the powder may be redissolved in a solvent to be described later, for example, and used as a solution.
又,於本發明的實施形態之樹脂組成物中,(A)成分的丙烯酸聚合物係可為複數種的特定共聚物之混合物。 Further, in the resin composition of the embodiment of the present invention, the acrylic polymer of the component (A) may be a mixture of a plurality of specific copolymers.
接著,說明苯酚酚醛清漆型的(A)成分之合成方法。 Next, a method of synthesizing the component (A) of the phenol novolak type will be described.
使環氧化苯酚酚醛清漆樹脂或環氧化甲酚酚醛清漆樹脂、與環己烯羧酸,在氯化苄基三乙銨等的觸媒之存在下,於80℃至150℃的溫度進行反應,可得到具有環己烯環的聚合物。此時,所用的溶劑,只要是溶解構成特定共聚物的單體與特定共聚物者,則沒有特別的限定。作為具體例,可舉出後述的溶劑。 The epoxidized phenol novolak resin or the epoxidized cresol novolac resin and the cyclohexene carboxylic acid are reacted at a temperature of 80 ° C to 150 ° C in the presence of a catalyst such as benzyltriethylammonium chloride. A polymer having a cyclohexene ring can be obtained. In this case, the solvent to be used is not particularly limited as long as it dissolves the monomer constituting the specific copolymer and the specific copolymer. As a specific example, the solvent mentioned later is mentioned.
於本發明的實施形態之樹脂組成物中,可作為(A)成分的使用之市售的環氧化苯酚酚醛清漆樹脂,例如有Epikote 152、同154(以上為油化Shell Epoxy(股)(現為日本環氧樹脂(股))製)、EPPN201及同202(以上為日本化藥(股)製)等的苯酚酚醛清漆型環氧樹脂等。又,作為市售的甲酚酚醛清漆型環氧樹脂之例,可舉出EOCN-102、EOCN-103S、EOCN-104S、EOCN-1020、EOCN-1025、EOCN-1027(以上為日本化藥(股)製)及Epikote 180S75(油化Shell Epoxy(股)(現為日本環氧樹脂(股))製)等的甲酚酚醛清漆型環氧樹脂等。 In the resin composition of the embodiment of the present invention, commercially available epoxidized phenol novolac resin which can be used as the component (A), for example, Epikote 152, and 154 (above, oiled Shell Epoxy) It is a phenol novolak type epoxy resin etc. which are made by Japan Epoxy Resin Co., Ltd., EPPN201, and 202 (above, Nippon Chemical Co., Ltd.). Further, examples of commercially available cresol novolac type epoxy resins include EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (the above are Japanese chemical drugs ( A cresol novolac type epoxy resin such as Epikote 180S75 (oiled Shell Epoxy (now manufactured by Japan Epoxy Resin Co., Ltd.)).
(B)成分 (B) component
本發明的實施形態之樹脂組成物中所含有的(B)成分,係下述式(1)所示的在末端具有環己烯環的化合物, The component (B) contained in the resin composition of the embodiment of the present invention is a compound having a cyclohexene ring at the terminal represented by the following formula (1).
式(1)中,R表示碳原子數1至20的有機基,X表示氫原子、甲基或鹵素原子。(B)成分之在末端具有環己烯環的化合物,係藉由使多官能環氧化合物與環己烯羧酸反應之方法、或使多官能醇化合物與環己烯羧醯氯或環己烯二羧酸酐反應之方法而獲得。 In the formula (1), R represents an organic group having 1 to 20 carbon atoms, and X represents a hydrogen atom, a methyl group or a halogen atom. a compound having a cyclohexene ring at the terminal of the component (B), which is a method of reacting a polyfunctional epoxy compound with a cyclohexene carboxylic acid, or a polyfunctional alcohol compound with cyclohexene carboxy fluorene or a cyclohexane Obtained by a method in which an enedicarboxylic anhydride is reacted.
作為(B)成分之在末端具有環己烯環的化合物之例,可舉出以下者。 Examples of the compound having a cyclohexene ring at the terminal of the component (B) include the following.
(C)成分 (C) component
本發明的實施形態之樹脂組成物中所含有的(C)成分係交聯劑。作為此交聯劑,例如可舉出環氧化合物、羥甲基化合物及異氰酸酯化合物等。 The component (C) which is contained in the resin composition of the embodiment of the present invention is a crosslinking agent. Examples of the crosslinking agent include an epoxy compound, a methylol compound, and an isocyanate compound.
當上述(A)成分或後述(D)成分為具有羥基的聚合物時,(C)成分較佳為羥甲基化合物或異氰酸酯化合物。又,當(A)成分或(D)成分為具有羧基的聚合物時,(C)成分較佳為環氧化合物、羥甲基化合物或異氰酸酯化合物。 When the component (A) or the component (D) described later is a polymer having a hydroxyl group, the component (C) is preferably a methylol compound or an isocyanate compound. Further, when the component (A) or the component (D) is a polymer having a carboxyl group, the component (C) is preferably an epoxy compound, a methylol compound or an isocyanate compound.
作為環氧化合物,例如可舉出三(2,3-環氧基丙基)異三聚氰酸酯、1,4-丁二醇二環氧丙基醚、1,2-環氧基-4-(環氧基乙基)環己烷、甘油三環氧丙基醚、二乙二醇二環氧丙基醚、2,6-二環氧丙基苯基環氧丙基醚、1,1,3-三[p-(2,3-環氧基丙氧基)苯基]丙烷、1,2-環己烷二羧酸二環氧 丙基酯、4,4’-亞甲基雙(N,N-二環氧丙基苯胺)、3,4-環氧基環己基甲基-3,4-環氧基環己烷羧酸酯、三羥甲基乙烷三環氧丙基醚、雙酚-A-二環氧丙基醚及季戊四醇聚環氧丙基醚等。 Examples of the epoxy compound include tris(2,3-epoxypropyl)isocyanate, 1,4-butanediol diepoxypropyl ether, and 1,2-epoxy- 4-(epoxyethyl)cyclohexane, glycerol triepoxypropyl ether, diethylene glycol diepoxypropyl ether, 2,6-diepoxypropyl phenylepoxypropyl ether, 1 , 1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diepoxy Propyl ester, 4,4'-methylenebis(N,N-diepoxypropylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylic acid Ester, trimethylolethane triepoxypropyl ether, bisphenol-A-diglycidyl ether, pentaerythritol polyepoxypropyl ether, and the like.
從取得容易之點看,環氧化合物亦可使用市售品的化合物。以下舉出其具體例(商品名),惟不受此等所限定。 例如,可舉出YH-434及YH434L(東都化成(股)製)等之具有胺基的環氧樹脂、Epolead GT-401、同GT-403、同GT-301、同GT-302、Celloxide 2021及Celloxide 3000(DAICEL化學工業(股)製)等之具有氧化環己烯的構造之環氧樹脂、Epikote 1001、同1002、同1003、同1004、同1007、同1009、同1010及同828(以上為油化Shell Epoxy(股)(現為日本環氧樹脂(股))製)等之雙酚A型環氧樹脂、Epikote 807(油化Shell Epoxy(股)(現為日本環氧樹脂(股))製)等之雙酚F型環氧樹脂、Denacol EX-252(Nagase Chemtex(股)製)、CY175、CY177、CY179、Araldite CY-182、同CY-192、同CY-184(以上為CIBA-GEIGY A.G(現為BASF)製)、Epiclon 200、同400(以上為大日本油墨化學工業(股)(現DIC(股))製)、Epikote 871、同872(以上為油化Shell Epoxy(股)(現為日本環氧樹脂(股))製)、ED-5661、ED-5662(以上為Celanese Coating(股)製)等之脂環式環氧樹脂、Denacol EX-611、同EX-612、同EX-614、同EX-622、同EX-411、同EX-512、同EX-522、同EX-421、同EX-313、同EX-314、同EX- 321(Nagase Chemtex(股)製)等之脂肪族聚環氧丙基醚等。 From the point of view of ease of use, a compound of a commercially available product can also be used as the epoxy compound. The specific examples (trade names) are given below, but are not limited by these. For example, an epoxy group having an amine group such as YH-434 and YH434L (manufactured by Tohto Kasei Co., Ltd.), Epolead GT-401, GT-403, GT-301, GT-302, and Celloxide 2021 may be mentioned. And an epoxy resin having a structure of cyclohexene oxide, such as Celloxide 3000 (manufactured by DAICEL Chemical Industry Co., Ltd.), Epikote 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 ( The above is a bisphenol A type epoxy resin such as oiled Shell Epoxy (now manufactured by Japan Epoxy Co., Ltd.), and Epikote 807 (oiled Shell Epoxy (now) (now Japanese epoxy resin ( )))) bisphenol F type epoxy resin, Denacol EX-252 (made by Nagase Chemtex), CY175, CY177, CY179, Araldite CY-182, same CY-192, same as CY-184 (above) It is CIBA-GEIGY AG (now BASF), Epiclon 200, 400 (above is Dainippon Ink Chemical Industry Co., Ltd. (now DIC)), Epikote 871, and 872 (above is Oiled Shell) Epoxy (currently manufactured by Nippon Epoxy Resin Co., Ltd.), ED-5661, ED-5662 (above: Celanese Coating Co., Ltd.), alicyclic epoxy resin, Denacol EX-611, same EX-612, same as EX-614, with EX-622, with EX-411 With EX-512, with EX-522, with EX-421, with EX-313, with EX-314, with EX- An aliphatic polyepoxypropyl ether such as 321 (manufactured by Nagase Chemtex Co., Ltd.).
又,作為至少具有二個環氧基的化合物,並沒有特別的限制,可使用具有環氧基的聚合物。作為如此具有環氧基的聚合物,例如可藉由使用具有環氧基的加成聚合性單體進行加成聚合而製造。作為一例,可舉出聚丙烯酸環氧丙酯與甲基丙烯酸環氧丙酯和甲基丙烯酸乙酯之共聚物、甲基丙烯酸環氧丙酯與苯乙烯和甲基丙烯酸2-羥乙酯之共聚物的加成聚合聚合物、或環氧酚醛清漆等的縮聚合聚合物等。 Further, the compound having at least two epoxy groups is not particularly limited, and a polymer having an epoxy group can be used. The polymer having such an epoxy group can be produced, for example, by addition polymerization using an addition polymerizable monomer having an epoxy group. As an example, a copolymer of polyacrylic acid glycidyl acrylate, glycidyl methacrylate and ethyl methacrylate, glycidyl methacrylate and styrene and 2-hydroxyethyl methacrylate may be mentioned. An addition polymerization polymer of a copolymer or a polycondensation polymer such as an epoxy novolac.
又,作為上述具有環氧基的聚合物,亦可藉由具有羥基的高分子化合物與環氧氯丙烷及環氧丙基甲苯磺酸酯等之具有環氧基的化合物之反應而製造。如此的聚合物之重量平均分子量,例如以聚苯乙烯換算為300至200,000。 Further, the polymer having an epoxy group may be produced by a reaction of a polymer compound having a hydroxyl group with a compound having an epoxy group such as epichlorohydrin or a epoxypropyl tosylate. The weight average molecular weight of such a polymer is, for example, 300 to 200,000 in terms of polystyrene.
作為可當作(C)成分使用的羥甲基化合物之例,可舉出甲氧基甲基化甘脲、甲氧基甲基化苯并胍胺及甲氧基甲基化蜜胺等。作為具體例,可舉出六甲氧基甲基蜜胺、四甲氧基甲基苯并胍胺、1,3,4,6-四(丁氧基甲基)甘脲、1,3,4,6-四(羥甲基)甘脲、1,3-雙(羥甲基)脲、1,1,3,3-四(丁氧基甲基)脲、1,1,3,3-四(甲氧基甲基)脲、1,3-雙(羥甲基)-4,5-二羥基-2-咪唑酮及1,3-雙(甲氧基甲基)-4,5-二甲氧基-2-咪唑酮等。又,作為市售品,可舉出三井CYTEC(股)製甲氧基甲基型蜜胺化合物(商品名Cymel 300、Cymel 301、Cymel 303、Cymel 350)、丁氧基甲基型蜜胺化合物(商品名Mycoat 506、Mycoat 508)、甘脲化合物(商品名 Cymel 1170、Powder link 1174)、甲基化脲樹脂(商品名UFR65)、丁基化尿素樹脂(商品名UFR300、U-VAN10S60、U-VAN10R、U-VAN11HV)、大日本油墨化學工業(股)(現DIC(股))製尿素/甲醛系樹脂(高縮合型,商品名Beckamine J-300S、Beckamine P-955、Beckamine N)等。 Examples of the methylol compound which can be used as the component (C) include methoxymethylated glycoluril, methoxymethylated benzoguanamine, and methoxymethylated melamine. Specific examples thereof include hexamethoxymethyl melamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(butoxymethyl) glycoluril, 1,3,4 ,6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3- Tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolidone and 1,3-bis(methoxymethyl)-4,5- Dimethoxy-2-imidazolidone and the like. Further, as a commercially available product, a methoxymethyl type melamine compound (trade name: Cymel 300, Cymel 301, Cymel 303, Cymel 350) manufactured by Mitsui CYTEC Co., Ltd., and a butoxymethyl melamine compound are mentioned. (trade name Mycoat 506, Mycoat 508), glycoluril compound (trade name) Cymel 1170, Powder link 1174), methylated urea resin (trade name UFR65), butylated urea resin (trade name UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV), Dainippon Ink Chemical Industry Co., Ltd. (current DIC (share)) urea/formaldehyde resin (high condensation type, trade name Beckamine J-300S, Beckamine P-955, Beckamine N).
又,作為異氰酸酯化合物之例,可舉出以下者。例如,作為在1分子中具有2個以上的異氰酸酯基之化合物,可舉出異佛爾酮二異氰酸酯、1,6-六亞甲基二異氰酸酯、亞甲基雙(4-環己基異氰酸酯)、三甲基六亞甲基二異氰酸酯等或此等的二聚物、三聚物、或此等與二醇類、三醇類、二胺類或三胺類之反應物。此等異氰酸酯化合物,為了提高在溶液中的保存安定性,較佳為使用經由封端劑所封端者。 Moreover, as an example of an isocyanate compound, the following are mentioned. For example, examples of the compound having two or more isocyanate groups in one molecule include isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylene bis(4-cyclohexyl isocyanate), Trimethylhexamethylene diisocyanate or the like, or a dimer, a trimer, or a reactant thereof with a glycol, a triol, a diamine or a triamine. These isocyanate compounds are preferably used by blocking with a blocking agent in order to improve storage stability in a solution.
作為封端劑,例如可舉出苯酚、鄰硝基苯酚、對氯苯酚、o-、m-或p-甲酚等的苯酚類、ε-己丙醯胺等的丙醯胺類、丙酮肟、甲基乙基酮肟、甲基異丁基酮肟、環己酮肟、苯乙酮肟及二苯基酮肟等的肟類、吡唑、3,5-二甲基吡唑、3-甲基吡唑等的吡唑類、十二烷硫醇及苯硫醇等的硫醇類。 Examples of the terminal blocking agent include phenol such as phenol, o-nitrophenol, p-chlorophenol, o-, m- or p-cresol, acrylamide such as ε-hexylamine, and acetone oxime. , methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime and diphenyl ketone oxime and the like, pyrazole, 3,5-dimethylpyrazole, 3 a thiol such as pyrazole such as methylpyrazole, dodecanethiol or benzenethiol.
作為(C)成分的化合物,可舉出以下的具體例。 Specific examples of the compound (C) include the following specific examples.
作為由異佛爾酮二異氰酸酯所衍生的異氰酸酯化合物,可舉出下述之例。 Examples of the isocyanate compound derived from isophorone diisocyanate include the following examples.
作為聚醚構造,例如可舉出來自聚乙二醇或聚丙二醇的2價基等。 The polyether structure may, for example, be a divalent group derived from polyethylene glycol or polypropylene glycol.
交聯劑亦可為使胺基的氫原子經羥甲基或烷氧基甲基所取代之蜜胺化合物、脲化合物、甘脲化合物或苯并胍胺化合物進行縮合而得之化合物。例如,可舉出美國專利第 6323310號中記載的由蜜胺化合物(商品名Cymel 303)與苯并胍胺化合物(商品名Cymel 1123)所製造的高分子量之化合物。 The crosslinking agent may be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound or a benzoguanamine compound in which a hydrogen atom of an amine group is substituted with a methylol group or an alkoxymethyl group. For example, the US patent A high molecular weight compound produced by a melamine compound (trade name Cymel 303) and a benzoguanamine compound (trade name Cymel 1123) as described in No. 6323310.
再者,作為(C)成分,亦可採用使用N-羥甲基丙烯醯胺、N-甲氧基甲基甲基丙烯醯胺、N-乙氧基甲基丙烯醯胺、N-丁氧基甲基甲基丙烯醯胺等之經羥甲基或烷氧基甲基取代之丙烯醯胺化合物或甲基丙烯醯胺化合物而製造的聚合物等。作為該聚合物,例如可舉出聚(N-丁氧基甲基丙烯醯胺)、N-丁氧基甲基丙烯醯胺與苯乙烯之共聚物、N-羥甲基甲基丙烯醯胺與甲基甲基丙烯酸酯之共聚物、N-乙氧基甲基甲基丙烯醯胺與甲基丙烯酸苄酯之共聚物及N-丁氧基甲基丙烯醯胺與甲基丙烯酸苄酯和甲基丙烯酸2-羥丙酯之共聚物等。如此的聚合物之重量平均分子量,例如以聚苯乙烯換算為1,000至500,000,較佳為2,000至200,000,更佳為3,000至150,000,特佳為3,000至50,000。 Further, as the component (C), N-methylol acrylamide, N-methoxymethyl methacrylamide, N-ethoxymethyl acrylamide, N-butoxy can also be used. A polymer produced by a hydroxymethyl or alkoxymethyl group-substituted acrylamide compound or a methacrylamide compound such as methyl methacrylamide. Examples of the polymer include poly(N-butoxymethyl acrylamide), a copolymer of N-butoxymethyl acrylamide and styrene, and N-methylol methacrylamide. Copolymer with methyl methacrylate, copolymer of N-ethoxymethyl methacrylamide and benzyl methacrylate, and N-butoxymethyl acrylamide and benzyl methacrylate a copolymer of 2-hydroxypropyl methacrylate or the like. The weight average molecular weight of such a polymer is, for example, 1,000 to 500,000 in terms of polystyrene, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, particularly preferably 3,000 to 50,000.
以上所述的交聯劑係可單獨或組合或2種以上而使用。 The above-mentioned crosslinking agents may be used singly or in combination of two or more kinds.
於本發明的實施形態之樹脂組成物中,(C)成分的交聯劑之含量,當使用(A)成分時,以(A)成分的100質量份為基礎,較佳為1至100質量份。又,當使用(B)成分時,以(B)成分與(D)成分的合計量100質量份為基礎,較佳為1至100質量份。該比例若過小,則由於硬化膜的耐溶劑性降低,配向性降低,或耐熱性降低。另一方面,上 述比例若過大,則配向性會降低,或保存安定性會降低。 In the resin composition of the embodiment of the present invention, the content of the crosslinking agent of the component (C) is preferably from 1 to 100 based on 100 parts by mass of the component (A) when the component (A) is used. Share. In addition, when the component (B) is used, it is preferably from 1 to 100 parts by mass based on 100 parts by mass of the total of the components (B) and (D). When the ratio is too small, the solvent resistance of the cured film is lowered, the alignment property is lowered, or the heat resistance is lowered. On the other hand, on If the ratio is too large, the alignment will be lowered, or the preservation stability will be lowered.
(D)成分 (D) component
本發明的實施形態之樹脂組成物中所含有的(D)成分係「其它聚合物」,是成為添加(B)成分用的黏結劑之聚合物(黏結劑聚合物)。此「其它聚合物」的種類係沒有特別的限定,但較佳為藉由具有熱交聯基,而自交聯,或與(C)成分的交聯劑反應者。作為熱交聯基,可舉出羧基、羥基、環氧基、氧雜環丁烷基、丙烯醯基及甲基丙烯醯基等。又,(D)成分的重量平均分子量以聚苯乙烯換算較佳為1,000至100,000。 The component (D) contained in the resin composition of the embodiment of the present invention is a polymer (adhesive polymer) which is a binder for adding the component (B). The type of the "other polymer" is not particularly limited, but is preferably self-crosslinking or reacting with a crosslinking agent of the component (C) by having a thermal crosslinking group. Examples of the thermal crosslinking group include a carboxyl group, a hydroxyl group, an epoxy group, an oxetanyl group, an acryloyl group, and a methacryl group. Further, the weight average molecular weight of the component (D) is preferably from 1,000 to 100,000 in terms of polystyrene.
作為其它聚合物的較佳例,可舉出含有下述式(2)所示之構造單位的聚酯樹脂、具有交聯基的丙烯酸聚合物、或下述式(3)所示的聚酯樹脂等。 Preferable examples of the other polymer include a polyester resin having a structural unit represented by the following formula (2), an acrylic polymer having a crosslinking group, or a polyester represented by the following formula (3). Resin, etc.
上述式(2)所示的聚合物係藉由下述的四羧酸二酐(式(i))與二醇化合物(式(ii)的聚合反應而獲得。 The polymer represented by the above formula (2) is obtained by a polymerization reaction of a tetracarboxylic dianhydride (formula (i)) and a diol compound (formula (ii)).
上述式(i)及式(ii)中,A表示以4個結合鍵鍵結於脂環式骨架或脂肪族骨架的4價有機基,B表示以2個結合鍵鍵結於脂環式骨架或脂肪族骨架的2價有機基。 In the above formulas (i) and (ii), A represents a tetravalent organic group bonded to an alicyclic skeleton or an aliphatic skeleton by four bonding bonds, and B represents an alicyclic skeleton bonded by two bonding bonds. Or a divalent organic group of an aliphatic skeleton.
於本發明的實施形態之樹脂組成物中,(B)成分與(D)成分的混合比較佳為5:95至50:50。(B)成分若少於此比例,則配向性會降低。另一方面,若過大,則耐溶劑性會 降低,或配向性會降低,而且成膜性亦會降低。再者,於不使特性降低的範圍內,(D)成分係可混合在(A)成分中。 In the resin composition of the embodiment of the present invention, the mixing of the component (B) and the component (D) is preferably from 5:95 to 50:50. If the component (B) is less than this ratio, the alignment property is lowered. On the other hand, if it is too large, solvent resistance will The reduction, or the alignment, is lowered, and the film formability is also lowered. Further, the component (D) may be mixed in the component (A) insofar as the properties are not lowered.
(E)成分 (E) component
本發明的實施形態之樹脂組成物亦可含有交聯觸媒當作(E)成分。在促進樹脂組成物的熱硬化性之點,(E)成分係有效。 The resin composition of the embodiment of the present invention may contain a crosslinking catalyst as the component (E). The component (E) is effective in promoting the thermosetting property of the resin composition.
例如,當樹脂組成物中所含有的羥基與羥甲基化合物反應時,在(E)成分的交聯觸媒中,酸或熱酸產生劑係有用。作為如此的酸或熱酸產生劑,可舉出含有磺酸基的化合物、鹽酸或其鹽,只要是在預烘烤或後烘烤時能熱分解而產生酸的化合物,即在80至250℃進行熱分解而產生酸的化合物,則沒有特別的限定。 For example, when a hydroxyl group contained in the resin composition is reacted with a methylol compound, an acid or a thermal acid generator is useful in the crosslinking catalyst of the component (E). Examples of such an acid or thermal acid generator include a compound containing a sulfonic acid group, hydrochloric acid or a salt thereof, as long as it is a compound which can be thermally decomposed to generate an acid during prebaking or postbaking, that is, at 80 to 250. The compound which thermally decomposes to generate an acid at ° C is not particularly limited.
作為上述酸的具體例,可舉出鹽酸、甲磺酸、乙磺酸、丙磺酸、丁磺酸、戊磺酸、辛磺酸、苯磺酸、對甲苯磺酸、樟腦磺酸、三氟甲烷磺酸、對苯酚磺酸、2-萘磺酸、三甲苯磺酸、對二甲苯-2-磺酸、間二甲苯-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、九氟丁烷-1-磺酸及十二基苯磺酸等的磺酸或其水合物或鹽等。 Specific examples of the acid include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, valeric acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, and the like. Fluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, trimethylbenzenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, 1H , 2H, 2H-perfluorooctane sulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, etc. Sulfonic acid or a hydrate or salt thereof.
又,作為熱酸產生劑,更可舉出雙(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、對硝基苄基甲苯磺酸酯、鄰硝基苄基甲苯磺酸酯、1,2,3-伸苯基三(甲基磺酸酯)、對甲苯磺酸吡啶鎓鹽、對甲苯磺酸嗎啉鎓鹽、對甲苯磺酸乙酯、對甲苯磺酸丙酯、對甲苯磺 酸丁酯、對甲苯磺酸異丁酯、對甲苯磺酸甲酯、對甲苯磺酸苯乙酯、氰甲基對甲苯磺酸酯、2,2,2-三氟乙基對甲苯磺酸酯、2-羥丁基對甲苯磺酸酯及N-乙基-4-甲苯磺醯胺等,還可舉出下式所示的化合物。 Further, examples of the thermal acid generator include bis(toluenesulfonyloxy)ethane, bis(toluenesulfonyloxy)propane, bis(toluenesulfonyloxy)butane, and p-nitrobenzyltoluene. Sulfonate, o-nitrobenzyl tosylate, 1,2,3-phenylphenyl tris(methylsulfonate), pyridinium p-toluenesulfonate, morpholinium p-toluenesulfonate, Ethyl tosylate, propyl p-toluenesulfonate, p-toluene Butyl acrylate, isobutyl p-toluenesulfonate, methyl p-toluenesulfonate, phenylethyl p-toluenesulfonate, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonic acid Examples of the ester, 2-hydroxybutyl p-toluenesulfonate, and N-ethyl-4-toluenesulfonamide include compounds represented by the following formulas.
本發明的實施形態之樹脂組成物中的(E)成分之含量,相對於(A)成分的100質量份,或相對於(B)成分與(D)成分的合計量100質量份而言,較佳為0.01至5質量份。(E)成分的含量若未達0.01質量份,則會看不到促進樹脂組成物的熱硬化性之效果。另一方面,若超過5質量份,則樹脂組成物的保存安定性會降低。 The content of the component (E) in the resin composition of the embodiment of the present invention is 100 parts by mass of the component (A) or 100 parts by mass based on the total amount of the component (B) and the component (D). It is preferably from 0.01 to 5 parts by mass. When the content of the component (E) is less than 0.01 parts by mass, the effect of promoting the thermosetting property of the resin composition is not observed. On the other hand, when it exceeds 5 mass parts, the storage stability of a resin composition will fall.
本發明的實施形態之樹脂組成物係可以溶解在溶劑中的溶液狀態使用。作為所用的溶劑,必須是溶解(A)成分或溶解(B)成分與(D)成分者。又,按照需要,亦可為溶解(C)成分者,或溶解(C)成分連同(E)成分者,或單獨溶解(E)成分者。再者,按照需要,可為溶解後述的其它添加劑者。若為具有該溶解能力的溶劑,則種類及構造等係沒有特別的限定。 The resin composition of the embodiment of the present invention can be used in the form of a solution dissolved in a solvent. As the solvent to be used, it is necessary to dissolve the component (A) or dissolve the component (B) and the component (D). Further, if necessary, those in which the component (C) is dissolved, or the component (C) is dissolved together with the component (E), or the component (E) is dissolved alone. Further, if necessary, those which dissolve other additives described later may be used. The type and structure of the solvent having such a dissolving ability are not particularly limited.
作為上述溶劑,例如可舉出乙二醇單甲基醚、乙二醇單乙基醚、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二乙二醇單甲基醚、二乙二醇單乙基醚、丙二醇、丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、丙二醇丙基醚乙酸酯、甲苯、二甲苯、甲基乙基酮、環戊酮、環己酮、2-庚酮、γ-丁內酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸甲酯、丙酮酸甲酯、丙酮酸乙酯、醋酸乙酯、醋酸丁酯、乳酸乙酯、乳酸丁酯、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺及N-甲基吡咯啶酮等。此等溶劑係可單獨或組合或2種以上而使用。 Examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, and diethylene glycol monomethyl ether. , diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, Cyclohexanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropanoate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2- Methyl hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate , methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide and N - methyl pyrrolidone or the like. These solvents may be used singly or in combination of two or more kinds.
再者,只要不損害本發明的效果,則本發明的實施形態之樹脂組成物視需要亦可含有矽烷偶合劑、界面活性劑、流變性調整劑、顏料、染料、保存安定劑、消泡劑及 抗氧化劑等。 In addition, the resin composition of the embodiment of the present invention may contain a decane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, and an antifoaming agent, as needed, as long as the effects of the present invention are not impaired. and Antioxidants, etc.
本發明的實施形態之樹脂組成物係含有(A)成分之具有環己烯環的聚合物、或(B)成分之在末端具有環己烯環的化合物中之任一者。 The resin composition of the embodiment of the present invention contains either a polymer having a cyclohexene ring of the component (A) or a compound having a cyclohexene ring at the terminal of the component (B).
又,本發明的實施形態之樹脂組成物係按照所欲而含有(C)成分之交聯劑。 Further, the resin composition of the embodiment of the present invention contains a crosslinking agent of the component (C) as desired.
另外,本發明的實施形態之樹脂組成物,當含有(B)成分時,係含有(D)成分之其它聚合物。 Further, when the resin composition of the embodiment of the present invention contains the component (B), it is another polymer containing the component (D).
再者,本發明的實施形態之樹脂組成物,係可含有(E)成分之交聯觸媒,而且可含有其它添加劑中的1種以上。 Furthermore, the resin composition of the embodiment of the present invention may contain a crosslinking catalyst of the component (E), and may contain one or more of other additives.
本發明的實施形態之樹脂組成物,係可將上述成分溶解於溶劑中,作為溶液使用。 In the resin composition of the embodiment of the present invention, the above components can be dissolved in a solvent and used as a solution.
本發明的實施形態之樹脂組成物的較佳例係如以下。 Preferred examples of the resin composition of the embodiment of the present invention are as follows.
[1]:以(A)成分的100質量份為基礎,含有1至100質量份的(C)成分之樹脂組成物。 [1]: A resin composition containing 1 to 100 parts by mass of the component (C) based on 100 parts by mass of the component (A).
[2]:以(B)成分與(D)成分的合計量100質量份為基礎,含有1至100質量份的(C)成分之樹脂組成物。 [2]: The resin composition of the component (C) is contained in an amount of 1 to 100 parts by mass based on 100 parts by mass of the total of the components (B) and (D).
[3]:以(A)成分的100質量份為基礎,含1至100質量份的(C)成分及溶劑之樹脂組成物。 [3]: a resin composition containing 1 to 100 parts by mass of the component (C) and a solvent based on 100 parts by mass of the component (A).
[4]:以(B)成分與(D)成分的合計量100質量份為基礎,含有1至100質量份的(C)成分及溶劑之樹脂組成物。 [4]: A resin composition containing 1 to 100 parts by mass of the component (C) and a solvent, based on 100 parts by mass of the total of the components (B) and (D).
[5]:以(A)成分的100質量份為基礎,含有1至100質量份的(C)成分、0.01至5質量份的(E)成分及溶劑之樹脂組成物。 [5]: A resin composition containing 1 to 100 parts by mass of the component (C), 0.01 to 5 parts by mass of the component (E), and a solvent, based on 100 parts by mass of the component (A).
[6]:以(B)成分與(D)成分的合計量100質量份為基礎,含有1至100質量份的(C)成分、0.01至5質量份的(E)成分及溶劑之樹脂組成物。 [6]: Based on 100 parts by mass of the total of the components (B) and (D), the resin composition contains 1 to 100 parts by mass of the component (C), 0.01 to 5 parts by mass of the component (E), and a solvent. Things.
使用本發明的實施形態之樹脂組成物作為溶液時,其配合比例及調製方法等係如以下。 When the resin composition of the embodiment of the present invention is used as a solution, the mixing ratio, the preparation method, and the like are as follows.
本發明的實施形態之樹脂組成物中的固體成分之比例,只要各成分均勻溶解於溶劑中,則沒有特別的限定,較佳為1至80質量%,更佳為3至60質量%,尤佳為5至40質量%。此處所謂的固體成分,就是自樹脂組成物的全部成分中去掉溶劑者。 The ratio of the solid content in the resin composition of the embodiment of the present invention is not particularly limited as long as the respective components are uniformly dissolved in the solvent, and is preferably from 1 to 80% by mass, more preferably from 3 to 60% by mass, particularly Good is 5 to 40% by mass. The solid component referred to herein is one in which the solvent is removed from all the components of the resin composition.
本發明的實施形態之樹脂組成物的調製方法係沒有特別的限定,例如可舉出將(A)成分、或(B)成分與(D)成分溶解於溶劑中,於此溶液中以指定的比例混合(C)成分、(E)成分,而成為均勻的溶液之方法。又,於此調製方法的適當階段中,視需要可更添加、混合其它添加劑。 The preparation method of the resin composition of the embodiment of the present invention is not particularly limited, and examples thereof include the component (A) or the component (B) and the component (D) dissolved in a solvent, and the solution is specified in the solution. A method in which a component (C) and a component (E) are mixed in proportion to form a uniform solution. Further, in an appropriate stage of the preparation method, other additives may be further added and mixed as needed.
於本發明的實施形態之樹脂組成物的調製時,可將在溶劑中聚合反應所得之聚合物的溶液直接使用。此時,於(A)成分、或(B)成分與(D)成分的溶液中,與前述同樣地,置入(C)成分、(E)成分等以成為均勻的溶液時,以調整濃度為目的,可追加投入溶劑。此時,可與聚合物之生成過程中所用的溶劑、樹脂組成物之調製時用於調整濃度的溶 劑相同或不同。 In the preparation of the resin composition of the embodiment of the present invention, a solution of a polymer obtained by polymerization in a solvent can be used as it is. In this case, in the solution of the component (A) or the component (B) and the component (D), in the same manner as described above, when the component (C) or the component (E) is placed to form a uniform solution, the concentration is adjusted. For the purpose, an additional solvent can be added. In this case, it can be used to adjust the concentration of the solvent and the resin composition used in the formation of the polymer. The agents are the same or different.
如上述所調製的樹脂組成物之溶液,較佳為用孔徑為0.2μm左右的過濾器等進行過濾後而使用。 The solution of the resin composition prepared as described above is preferably used after being filtered with a filter having a pore diameter of about 0.2 μm or the like.
可使用本發明的實施形態之樹脂組成物,藉由如以下的方法來形成塗膜。 The resin film of the embodiment of the present invention can be used to form a coating film by the following method.
首先,於基板或薄膜等上,藉由旋轉塗佈、流動塗佈、輥塗佈、狹縫塗佈、於狹縫之後的旋轉塗佈、噴墨塗佈或印刷等來塗佈樹脂組成物。其次,可藉由熱板或烘箱等進行預備乾燥(預烘烤),而形成塗膜。然後,加熱處理(後烘烤)此塗膜,而形成硬化膜。 First, a resin composition is applied onto a substrate, a film, or the like by spin coating, flow coating, roll coating, slit coating, spin coating after slit, inkjet coating, printing, or the like. . Next, preliminary drying (prebaking) can be performed by a hot plate or an oven to form a coating film. Then, this coating film is heat-treated (post-baking) to form a cured film.
作為塗佈樹脂組成物的基板,例如可使用矽/二氧化矽被覆基板、氮化矽基板、玻璃基板、石英基板及ITO基板等。又,例如亦可使用被覆有鋁、鉬或鉻等的金屬之基板。再者,例如也可使用三乙醯纖維素薄膜、聚酯薄膜及丙烯酸薄膜等的樹脂薄膜等作為基板。 As the substrate to 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 may be used as the substrate.
作為形成塗膜用的預烘烤之條件,例如可採用由溫度70至160℃、時間0.3至60分鐘的範圍中適宜選出的加熱溫度及加熱時間。加熱溫度及加熱時間較佳為在80至140℃進行0.5至10分鐘。 As the prebaking conditions for forming the coating film, for example, a heating temperature and a heating time which are suitably selected from a temperature of 70 to 160 ° C and a time of 0.3 to 60 minutes can be employed. The heating temperature and heating time are preferably from 0.5 to 10 minutes at 80 to 140 °C.
後烘烤係按照加熱方法等,採用由溫度140至250℃的範圍中適宜選出的加熱溫度。又,加熱時間亦同樣,例如在熱板上時為5至30分鐘,在烘箱中時為30至90分 鐘等。 The post-baking is carried out according to a heating method or the like, and a heating temperature suitably selected from the range of temperature 140 to 250 ° C is employed. Also, the heating time is the same, for example, 5 to 30 minutes on a hot plate and 30 to 90 minutes in an oven. Clock and so on.
在如上述的條件下,使本發明的實施形態之樹脂組成物硬化,可充分覆蓋彩色濾光片(CF)等所致的基板之階差而平坦化,同時可形成具有高透明性的硬化膜。再者,硬化膜的膜厚例如可為0.1至30μm,可考慮所使用的基板之階差或光學、電的性質來適宜選擇。 When the resin composition of the embodiment of the present invention is cured under the above-described conditions, the step of the substrate due to the color filter (CF) or the like can be sufficiently covered to be flattened, and hardening with high transparency can be formed. membrane. Further, the film thickness of the cured film may be, for example, 0.1 to 30 μm, and may be appropriately selected in consideration of the step difference of the substrate to be used or the optical or electrical properties.
如上述所得之硬化膜,係可藉由進行摩擦處理而作為使液晶配向材料配向,即是使具有液晶性的分子配向之液晶配向層的機能。 The cured film obtained as described above can be used as a function of aligning a liquid crystal alignment material by rubbing treatment, that is, a liquid crystal alignment layer in which molecules having liquid crystallinity are aligned.
摩擦處理的條件一般係使用旋轉速度300至1,000rpm、輸送速度10至80mm/秒、壓入量0.1至1mm的條件。 於摩擦處理後,藉由使用純水等的超音波洗淨,去除摩擦所發生的殘渣。 The conditions of the rubbing treatment are generally those using a rotation speed of 300 to 1,000 rpm, a conveying speed of 10 to 80 mm/sec, and a press-in amount of 0.1 to 1 mm. After the rubbing treatment, the residue generated by the friction is removed by washing with ultrasonic waves such as pure water.
於如此所形成的液晶配向層上,塗佈位相差材料後,加熱到液晶的相轉移溫度為止,而使位相差材料成為液晶狀態。其次,若將此光硬化,則可形成作為具有光學異向性的層之位相差材料。 After the phase difference material is applied onto the liquid crystal alignment layer thus formed, the phase difference material is heated to the phase transition temperature of the liquid crystal, and the phase difference material is brought into a liquid crystal state. Next, if the light is hardened, a phase difference material which is a layer having optical anisotropy can be formed.
作為位相差材料,例如使用具有聚合性基的液晶單體、或含有其的組成物等。當形成有液晶配向層的基材為薄膜時,適用作為光學異向性薄膜。作為如此的位相差材料,有具有水平配向、膽固醇配向、垂直配向、混合配向、二軸配向等的配向性者,可各自按照需要的位相差分別使用。 As the phase difference material, for example, a liquid crystal monomer having a polymerizable group, a composition containing the same, or the like is used. When the substrate on which the liquid crystal alignment layer is formed is a film, it is suitably used as an optical anisotropic film. As such a phase difference material, there is an alignment having a horizontal alignment, a cholesterol alignment, a vertical alignment, a mixed alignment, a biaxial alignment, and the like, and each of them may be used in accordance with a desired phase difference.
又,將具有如上述所形成的液晶配向層之2片基板, 隔著間隔物,以液晶配向層彼此呈相向的方式貼合後,在此等基板之間注入液晶,亦可成為液晶已配向的液晶顯示元件。 Moreover, the two substrates having the liquid crystal alignment layer formed as described above, After the spacers are bonded to each other such that the liquid crystal alignment layers face each other, liquid crystal is injected between the substrates, and the liquid crystal display elements in which the liquid crystals are aligned may be used.
如此地,本發明的實施形態之樹脂組成物係可適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 embodiment of the present invention can be suitably used for constituting various optical anisotropic films or liquid crystal display elements.
另外,本發明的實施形態之樹脂組成物,亦適用作為形成薄膜電晶體(TFT)型液晶顯示元件及有機EL元件等各種顯示器中的保護膜、平坦化膜、絕緣膜等硬化膜之材料。特別地,除了適合作為彩色濾光片(CF)的罩面材(CF罩面層),還適合作為TFT型液晶元件的層間絕緣膜、或有機EL元件的絕緣膜等。 In addition, the resin composition of the embodiment of the present invention is also used as a material for forming a cured film such as a protective film, a flattening film, or an insulating film in various displays such as a thin film transistor (TFT) liquid crystal display device and an organic EL device. In particular, it is suitable as an interlayer insulating film of a TFT-type liquid crystal element, an insulating film of an organic EL element, or the like, in addition to a cover material (CF overcoat layer) suitable as a color filter (CF).
使用本發明的實施形態之樹脂組成物作為CF罩面材時,所得之CF罩面層不僅可覆蓋彩色濾光片的階差而平坦化,而且亦作為液晶配向材料的機能。因此,可作為具有配向性的CF罩面層使用。 When the resin composition of the embodiment of the present invention is used as a CF cover material, the obtained CF overcoat layer can be planarized not only by covering the step of the color filter but also as a function of the liquid crystal alignment material. Therefore, it can be used as an oriented CF overcoat layer.
圖1係本發明的實施形態之液晶胞100的示意構成圖。於此圖中,液晶層108係被夾持在2片基板101、111之間。於基板111上形成有ITO110與配向膜109。 又,於基板101上,依順序形成有彩色濾光片102、CF罩面層103、位相差材料105、ITO106與配向膜107。此時,由於CF罩面層103亦作為配向膜的機能,故可以不需要對應於圖2的配向膜204之膜。 Fig. 1 is a schematic configuration diagram of a liquid crystal cell 100 according to an embodiment of the present invention. In the figure, the liquid crystal layer 108 is sandwiched between the two substrates 101, 111. An ITO 110 and an alignment film 109 are formed on the substrate 111. Further, on the substrate 101, a color filter 102, a CF overcoat layer 103, a phase difference material 105, an ITO 106, and an alignment film 107 are formed in this order. At this time, since the CF overcoat layer 103 also functions as an alignment film, a film corresponding to the alignment film 204 of FIG. 2 may not be required.
以下舉出實施例來更詳細說明本發明,惟本發明係不受此等實施例所限定。 The invention is illustrated in more detail below by the examples, but the invention is not limited by the examples.
以下實施例中所用的縮寫符號之意思係如下。 The abbreviations used in the following examples are as follows.
HEMA:甲基丙烯酸2-羥乙酯 HEMA: 2-hydroxyethyl methacrylate
MAA:甲基丙烯酸 MAA: Methacrylic acid
MMA:甲基丙烯酸甲酯 MMA: Methyl methacrylate
GMA:甲基丙烯酸環氧丙酯 GMA: glycidyl methacrylate
CHMI:N-環己基馬來醯亞胺 CHMI: N-cyclohexylmaleimide
AIBN:α,α’-偶氮雙異丁腈 AIBN: α,α'-azobisisobutyronitrile
BGOP;4,4’-雙環氧丙氧基苯基 BGOP; 4,4'-diglycidoxyphenyl
CHECA:環己烯-4-羧酸 CHECA: cyclohexene-4-carboxylic acid
BA:苯甲酸 BA: Benzoic acid
CHCA;環己烷羧酸 CHCA; cyclohexanecarboxylic acid
CHEDA:環己烯-4,5-二羧酸酐 CHEDA: cyclohexene-4,5-dicarboxylic anhydride
BPAGE:雙酚A二環氧丙基醚 BPAGE: bisphenol A diglycidyl ether
CHDCA:環己烷二羧酸 CHDCA: cyclohexanedicarboxylic acid
PVA:聚乙烯醇 PVA: polyvinyl alcohol
HBPDA:3,3’-4,4’-雙環己基四羧酸二酐 HBPDA: 3,3'-4,4'-dicyclohexyltetracarboxylic dianhydride
HBPA:氫化雙酚A HBPA: hydrogenated bisphenol A
BTEAC:氯化苄基三乙銨 BTEAC: benzyltriethylammonium chloride
GT4:DAICEL化學工業(股)製Epolead GT-401(製品名)(化合物名:環氧化丁烷四羧酸四(3-環己烯基甲基)修飾ε-己內酯) GT4: Epolead GT-401 (product name) manufactured by DAICEL Chemical Industry Co., Ltd. (Compound name: epoxidized butane tetracarboxylic acid tetrakis(3-cyclohexenylmethyl) modified ε-caprolactone)
CEL:DAICEL化學工業(股)製Celloxide P-2021(製品名)(化合物名:3,4-環氧基環己烯基甲基-3’,4’-環氧基環己烯羧酸酯) CEL: Celloxide P-2021 (product name) manufactured by DAICEL Chemical Industry Co., Ltd. (Compound name: 3,4-epoxycyclohexenylmethyl-3', 4'-epoxycyclohexene carboxylate )
TMGU:1,3,4,6-四(甲氧基甲基)甘脲 TMGU: 1,3,4,6-tetrakis(methoxymethyl)glycoluril
PWL;Powder link 1174(三井CYTEC(股)製) PWL; Powder link 1174 (Mitsui CYTEC (share) system)
PTSA:對甲苯磺酸1水合物 PTSA: p-toluenesulfonic acid monohydrate
CHN:環己酮 CHN: cyclohexanone
PGMEA:丙二醇單甲基醚乙酸酯 PGMEA: propylene glycol monomethyl ether acetate
PGME:丙二醇單甲基醚 PGME: propylene glycol monomethyl ether
NMP:N-甲基吡咯啶酮 NMP: N-methylpyrrolidone
依照以下合成例所得之聚合物的數量平均分子量及重量平均分子量,係使用日本分光(股)製GPC裝置(Shodex(註冊商標)管柱KF803L及KF804L),於溶析溶劑四氫呋喃以1mL/分鐘流量在管柱中(管柱溫度40℃)流動的溶離條件下測定。再者,下述的數量平均分子量(以下 稱為Mn)及重量平均分子量(以下稱為Mw)係以聚苯乙烯換算值表示。 According to the number average molecular weight and the weight average molecular weight of the polymer obtained in the following synthesis examples, a GPC apparatus (Shodex (registered trademark) column KF803L and KF804L) manufactured by JASCO Corporation was used, and a flow rate of 1 mL/min in a solvent of tetrahydrofuran was used. It was measured under the dissolution conditions in which the column was flowed (column temperature 40 ° C). Furthermore, the following number average molecular weight (below The weight average molecular weight (hereinafter referred to as Mw) and the weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.
將GMA 18.4g、HEMA 4.6g、AIBN 1.1g溶解於PGMEA 65.1g中,在80℃使反應20小時而得到丙烯酸聚合物溶液(固體成分濃度27質量%)(P1)。所得之丙烯酸聚合物的Mn為4,940,Mw為9,090。 GMA 18.4 g, HEMA 4.6 g, and AIBN 1.1 g were dissolved in PGMEA 65.1 g, and the reaction was allowed to proceed at 80 ° C for 20 hours to obtain an acrylic polymer solution (solid content concentration: 27% by mass) (P1). The obtained acrylic polymer had an Mn of 4,940 and a Mw of 9,090.
於P1的溶液25.0g中,加入CHECA 4.34g、PGMEA 12.0g、BTEAC 0.083g,在120℃使反應10小時,而得到具有環己烯環的聚合物(固體成分濃度27質量%)(P2)。所得之丙烯酸聚合物的Mn為8,240,Mw為19,440。 To 25.0 g of a solution of P1, 4.34 g of CHECA, 12.0 g of PGMEA, and 0.083 g of BTEAC were added, and the reaction was carried out at 120 ° C for 10 hours to obtain a polymer having a cyclohexene ring (solid content concentration: 27% by mass) (P2). . The obtained acrylic polymer had an Mn of 8,240 and a Mw of 19,440.
於市售的PVA(Mw31,000)3.30g中,加入CHEDA 7.10g、PGMEA 31.6g、BTEAC 0.125g,在120℃使反應10小時,而得到具有環己烯環的聚合物(固體成分濃度25質量%)(P3)。所得之乙烯基聚合物的Mn為47,720,Mw為111,303。 To a commercially available PVA (Mw31,000) 3.30 g, CHEDA 7.10 g, PGMEA 31.6 g, and BTEAC 0.125 g were added, and the reaction was carried out at 120 ° C for 10 hours to obtain a polymer having a cyclohexene ring (solid content concentration 25). Mass%) (P3). The obtained vinyl polymer had an Mn of 47,720 and a Mw of 111,303.
於BGOP 12.0g中,加入CHECA 7.69g、PGMEA 53.6g、BTEAC 0.14g,在120℃使反應10小時,而得到末端具有環己烯環的化合物(固體成分濃度27質量%)(B1)。 In BGOP 12.0g, add CHECA 7.69g, PGMEA 53.6 g and BTEAC 0.14 g were reacted at 120 ° C for 10 hours to obtain a compound having a cyclohexene ring at the end (solid content concentration: 27% by mass) (B1).
於CEL 10.0g中,加入CHECA 9.62g、PGMEA 53.5g、BTEAC 0.18g,在120℃使反應10小時,而得到末端具有環己烯環的化合物(固體成分濃度27質量%)(B2)。 In a CEL 10.0 g, 9.62 g of CHECA, 53.5 g of PGMEA, and 0.18 g of BTEAC were added, and the reaction was carried out at 120 ° C for 10 hours to obtain a compound having a cyclohexene ring at the end (solid content concentration: 27% by mass) (B2).
於GT4 6.0g中,加入CHECA 3.30g、PGMEA 46.7g、BTEAC 0.06g,在120℃使反應10小時,而得到末端具有環己烯環的化合物(固體成分濃度27質量%)(B3)。 In GT4 6.0g, CHECA 3.30 g, PGMEA 46.7 g, and BTEAC 0.06 g were added, and the reaction was carried out at 120 ° C for 10 hours to obtain a compound having a cyclohexene ring at the end (solid content concentration: 27% by mass) (B3).
使HBPDA 12.0g、HBPA 10.2g、BTEAC 0.22g在PGMEA 54.48g中,於125℃反應19小時,而得到聚酯溶液(固體成分濃度:30.0質量%)(P4)。所得之聚酯的Mn為1,980,Mw為3,500。 12.0 g of HBPDA, 10.2 g of HBPA, and 0.22 g of BTEAC were reacted in PGMEA 54.48 g at 125 ° C for 19 hours to obtain a polyester solution (solid content concentration: 30.0% by mass) (P4). The obtained polyester had an Mn of 1,980 and a Mw of 3,500.
將MAA 2.5g、MMA 9.2g、HEMA 5.0g、作為聚合觸 媒的AIBN 0.2g溶解於PGME 50.7g中,在70℃使反應20小時,而得到丙烯酸共聚物溶液(固體成分濃度25質量%)(P5)。所得之丙烯酸共聚物的Mn為19,600,Mw為45,200。 MAA 2.5g, MMA 9.2g, HEMA 5.0g, as a polymerization touch 0.2 g of AIBN of the medium was dissolved in 50.7 g of PGME, and the reaction was allowed to proceed at 70 ° C for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 25% by mass) (P5). The obtained acrylic copolymer had an Mn of 19,600 and a Mw of 45,200.
於P1的溶液25.0g中,加入BA 4.21g、PGMEA 11.6g、BTEAC 0.083g,在120℃使反應10小時,而得到丙烯酸聚合物(固體成分濃度27質量%)(P6)。所得之丙烯酸聚合物的Mn為7,920,Mw為17,940。 To 25.0 g of a solution of P1, 4.21 g of BA, 11.6 g of PGMEA, and 0.083 g of BTEAC were added, and the reaction was carried out at 120 ° C for 10 hours to obtain an acrylic polymer (solid content concentration: 27% by mass) (P6). The obtained acrylic polymer had an Mn of 7,920 and a Mw of 17,940.
於P1的溶液25.0g中,加入CHCA 4.41g、PGMEA 12.2g、BTEAC 0.083g,在120℃使反應10小時,而得到具有環己烯環的丙烯酸聚合物(固體成分濃度27質量%)(P7)。所得之丙烯酸聚合物的Mn為7,620,Mw為17,860。 To 25.0 g of a solution of P1, 4.41 g of CHCA, 12.2 g of PGMEA, and 0.083 g of BTEAC were added, and the reaction was carried out at 120 ° C for 10 hours to obtain an acrylic polymer having a cyclohexene ring (solid content concentration: 27% by mass) (P7). ). The obtained acrylic polymer had an Mn of 7,620 and a Mw of 17,860.
於CEL 10.0g中,加入CHCA 9.62g、PGMEA 53.5g、BTEAC 0.18g,在120℃使反應10小時,而得到在末端具有環己烷環的化合物(固體成分濃度27質量%)(B4)。 Into CEL 10.0 g, 9.62 g of CHCA, 53.5 g of PGMEA, and 0.18 g of BTEAC were added, and the reaction was carried out at 120 ° C for 10 hours to obtain a compound having a cyclohexane ring at the terminal (solid content concentration: 27% by mass) (B4).
將CHMI 4.0g、HEMA 6.0g、作為聚合觸媒的AIBN 0.5g溶解於PGMEA 24.5g中,在80℃使反應20小時,而得到丙烯酸共聚物溶液(固體成分濃度30質量%)(P8)。所得之丙烯酸共聚物的Mn為3,500,Mw為7,500。 5.0 g of CHMI, 6.0 g of HEMA, and 0.5 g of AIBN as a polymerization catalyst were dissolved in 24.5 g of PGMEA, and the reaction was allowed to proceed at 80 ° C for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 30% by mass) (P8). The obtained acrylic copolymer had an Mn of 3,500 and a Mw of 7,500.
於P8的溶液50.0g中,加入CHEDA 7.87g、PGMEA 22.9g、BTEAC 0.077g,在120℃使反應10小時,而得到具有環己烯環的聚合物(固體成分濃度30質量%)(P9)。所得之丙烯酸聚合物的Mn為8,243,Mw為24,990。 To 50.0 g of a solution of P8, 7.87 g of CHEDA, 22.9 g of PGMEA, and 0.077 g of BTEAC were added, and the reaction was carried out at 120 ° C for 10 hours to obtain a polymer having a cyclohexene ring (solid content concentration: 30% by mass) (P9) . The obtained acrylic polymer had an Mn of 8,243 and a Mw of 24,990.
將BPAGE 15.0g、CHDCA 8.35g、BTEAC 0.10g溶解於PGMEA 54.71g中,在120℃使反應20小時,而得到聚酯溶液(固體成分濃度:30.0質量%)(P10)。所得之聚酯的Mn為3,650,Mw為9,060。 15.0 g of BPAGE, 8.35 g of CHDCA, and 0.10 g of BTEAC were dissolved in 54.71 g of PGMEA, and the reaction was carried out at 120 ° C for 20 hours to obtain a polyester solution (solid content concentration: 30.0% by mass) (P10). The obtained polyester had an Mn of 3,650 and a Mw of 9,060.
於P10的溶液50.0g中,加入CHEDA 6.86g、PGMEA 16.2g,在120℃使反應15小時,而得到具有環己烯環的聚合物(固體成分濃度30質量%)(P11)。所得之聚酯的Mn為6,960,Mw為44,000。 To 50.0 g of a solution of P10, 6.86 g of CHEDA and 16.2 g of PGMEA were added, and the reaction was carried out at 120 ° C for 15 hours to obtain a polymer having a cyclohexene ring (solid content concentration: 30% by mass) (P11). The obtained polyester had an Mn of 6,960 and a Mw of 44,000.
以表1所示的組成,調製實施例1至實施例8及比較例1至比較例3的各組成物,對於各組成物進行耐溶劑性、透過率及配向性的評價。 Each of the compositions of Examples 1 to 8 and Comparative Examples 1 to 3 was prepared in the compositions shown in Table 1, and the composition was evaluated for solvent resistance, transmittance, and alignment.
使用旋塗機,將實施例1至實施例8及比較例1至比較例3的各組成物塗佈於矽晶圓上後,在溫度100℃的熱板上進行120秒的預烘烤,而形成膜厚1.1μm的塗膜。膜厚係使用FILMETRICS公司製F20來測定。將此塗膜在溫度230℃的熱風循環式烘箱中後烘烤30分鐘,而形成膜 厚1.0μm的硬化膜。 Each of the compositions of Examples 1 to 8 and Comparative Examples 1 to 3 was applied onto a ruthenium wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C for 120 seconds. On the other hand, a coating film having a film thickness of 1.1 μm was formed. The film thickness was measured using F20 manufactured by FILMETRICS. The film was post-baked in a hot air circulating oven at a temperature of 230 ° C for 30 minutes to form a film. A cured film having a thickness of 1.0 μm.
接著,將此硬化膜浸漬在CHN或NMP中60秒後,各自在溫度100℃乾燥60秒,測定膜厚。將在CHN或NMP浸漬後無膜厚變化者當作○,將在浸漬後看到膜厚的減少者當作×。 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, and the film thickness was measured. The change in the film thickness after immersion in CHN or NMP was regarded as ○, and the decrease in film thickness after immersion was regarded as ×.
使用旋塗機,將實施例1至實施例8及比較例1至比較例3的各組成物塗佈於石英基板上後,在溫度100℃的熱板上進行120秒的預烘烤,而形成膜厚1.0μm的塗膜。 膜厚係使用FILMETRICS公司製F20來測定。將此塗膜在溫度230℃的熱風循環式烘箱中後烘烤30分鐘,而形成硬化膜。 Each of the compositions of Examples 1 to 8 and Comparative Examples 1 to 3 was applied onto a quartz substrate by a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C for 120 seconds. A coating film having a film thickness of 1.0 μm was formed. The film thickness was measured using F20 manufactured by FILMETRICS. The coating film was post-baked in a hot air circulating oven at a temperature of 230 ° C for 30 minutes to form a cured film.
接著,對於此硬化膜,使用紫外線可見分光光度計((股)島津製作所製SHIMADSU UV-2550型號),測定波長400nm時的透過率。 Next, the transmittance of the cured film was measured using a UV-visible spectrophotometer (SHIMADSU UV-2550 model manufactured by Shimadzu Corporation) at a wavelength of 400 nm.
使用旋塗機,將實施例1至實施例8及比較例1至比較例3的各組成物塗佈於ITO基板上後,在溫度100℃的熱板上進行120秒的預烘烤,而形成膜厚2.8μm的塗膜。 膜厚係使用FILMETRICS公司製F20來測定。然後,將此膜在溫度200℃的熱風循環式烘箱中後烘烤30分鐘,而形成硬化膜。 Each of the compositions of Examples 1 to 8 and Comparative Examples 1 to 3 was applied onto an ITO substrate by a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C for 120 seconds. A coating film having a film thickness of 2.8 μm was formed. The film thickness was measured using F20 manufactured by FILMETRICS. Then, the film was post-baked in a hot air circulating oven at a temperature of 200 ° C for 30 minutes to form a cured film.
接著,以旋轉速度400rpm、輸送速度30mm/秒、壓入量0.4mm,摩擦處理硬化膜。用純水,以超音波洗淨經摩擦處理的基板5分鐘。接著,使用旋塗機,在此基板上塗佈由液晶單體所成的位相差材料,然後在80℃的熱板上進行60秒的預烘烤,而形成膜厚1.4μm的塗膜。接著,對此基板上的塗膜,在氮氣環境下,以1,000mJ/cm2的光進行曝光,以使位相差材料硬化。以偏向板夾住所製作的基板,用光學顯微鏡確認配向性。將在交叉尼科耳狀態下無漏光者當作○,將發生漏光者當作×。 Next, the cured film was rubbed at a rotation speed of 400 rpm, a conveyance speed of 30 mm/sec, and a press-in amount of 0.4 mm. The rubbed substrate was washed with pure water for 5 minutes with pure water. Next, a phase difference material made of a liquid crystal monomer was applied onto the substrate by a spin coater, and then prebaked on a hot plate at 80 ° C for 60 seconds to form a coating film having a film thickness of 1.4 μm. Next, the coating film on the substrate was exposed to light of 1,000 mJ/cm 2 under a nitrogen atmosphere to harden the phase difference material. The prepared substrate was sandwiched by a deflecting plate, and the alignment was confirmed by an optical microscope. The person who has no light leakage in the crossed Nicols is regarded as ○, and the person who has light leakage is regarded as ×.
使用旋塗機,將實施例1至實施例8及比較例1至比較例3的各組成物塗佈於矽晶圓上後,在溫度100℃的熱板上進行120秒的預烘烤,而形成膜厚1.1μm的塗膜。膜厚係使用FILMETRICS公司製F20來測定。然後,將此膜在溫度230℃的熱風循環式烘箱中後烘烤30分鐘,而形成膜厚1.0μm的硬化膜。 Each of the compositions of Examples 1 to 8 and Comparative Examples 1 to 3 was applied onto a ruthenium wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C for 120 seconds. On the other hand, a coating film having a film thickness of 1.1 μm was formed. The film thickness was measured using F20 manufactured by FILMETRICS. Then, this film was post-baked in a hot air circulating oven at a temperature of 230 ° C for 30 minutes to form a cured film having a film thickness of 1.0 μm.
接著,對此硬化膜,垂直照射313nm的直線偏光。 其次,更將硬化膜在溫度230℃的3小時熱風循環式烘箱中培燒,測定與後烘烤後的狀態之色差Ea*b*。 Next, this cured film was vertically irradiated with linearly polarized light of 313 nm. Next, the cured film was fired in a hot air circulating oven at a temperature of 230 ° C for 3 hours, and the color difference Ea*b* in the state after post-baking was measured.
彙總以上的評價,顯示於以下的表2中。 The above evaluations are summarized and shown in Table 2 below.
由實施例1至實施例8的組成物所形成的硬化膜,係液晶的配向性優異。因此,可知實施例1至實施例8的組成物係可形成優異的液晶配向材料。此外,耐熱性與透明性高,對於CHN及中的NMP的任一者,亦看到耐性。 The cured film formed of the compositions of Examples 1 to 8 is excellent in the alignment property of the liquid crystal. Therefore, it is understood that the compositions of Examples 1 to 8 can form an excellent liquid crystal alignment material. Further, heat resistance and transparency are high, and resistance is also observed for any of CHN and NMP.
另一方面,由比較例1至比較例3的組成物所形成的硬化膜,係液晶完全沒有配向,或以偏光顯微鏡觀察係看到漏光。 On the other hand, in the cured film formed of the compositions of Comparative Example 1 to Comparative Example 3, the liquid crystal was completely unaligned, or light leakage was observed by a polarizing microscope.
如以上,可知由本發明的樹脂組成物所得之硬化膜,係具有高的液晶配向性能,而且具有透光性、耐溶劑性及耐熱性。因此,可知藉由本發明的樹脂組成物,可提供上述諸特性優異之硬化膜,即液晶配向材料,更且可形成位相差材料。 As described above, it is understood that the cured film obtained from the resin composition of the present invention has high liquid crystal alignment properties and has light transmissivity, solvent resistance, and heat resistance. Therefore, it is understood that the resin composition of the present invention can provide a cured film having excellent properties as described above, that is, a liquid crystal alignment material, and can further form a phase difference material.
本發明的樹脂組成物係非常適用作為光學異向性薄膜或液晶顯示元件的液晶配向層,更且亦適合作為形成薄膜電晶體(TFT)型液晶顯示元件或有機EL元件等的各種顯示器中的保護膜、平坦化膜及絕緣膜等硬化膜之材料,尤其TFT型液晶元件的層間絕緣膜、彩色濾光片的保護膜或有機EL元件的絕緣膜等之材料。 The resin composition of the present invention is very suitable as a liquid crystal alignment layer for an optically anisotropic film or a liquid crystal display element, and is also suitable as a display for forming a thin film transistor (TFT) type liquid crystal display element or an organic EL element. A material of a cured film such as a protective film, a planarizing film, or an insulating film, in particular, an interlayer insulating film of a TFT liquid crystal element, a protective film of a color filter, or an insulating film of an organic EL element.
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