TW201406799A - Photocurable resin composition, image display device, and method for producing image display device - Google Patents
Photocurable resin composition, image display device, and method for producing image display device Download PDFInfo
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- 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
- G02F1/133308—Support structures for LCD panels, e.g. frames or bezels
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- 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
- G02F1/133308—Support structures for LCD panels, e.g. frames or bezels
- G02F1/133331—Cover glasses
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- 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
- G02F2202/00—Materials and properties
- G02F2202/02—Materials and properties organic material
- G02F2202/022—Materials and properties organic material polymeric
- G02F2202/023—Materials and properties organic material polymeric curable
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- 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
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
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Abstract
Description
本發明是關於一種光硬化性樹脂組成物、使用該樹脂組成物之影像顯示用裝置及該影像顯示用裝置之製造方法,該光硬化性樹脂組成物可用於防止影像顯示用裝置破裂、緩和應力及撞擊,且透明性優異。 The present invention relates to a photocurable resin composition, an image display device using the resin composition, and a method for producing the image display device, wherein the photocurable resin composition can be used to prevent image display device from rupturing and alleviating stress And impact, and excellent transparency.
作為配備有影像顯示用面板之代表性的影像顯示用裝置,可舉例如液晶顯示用裝置。作為液晶顯示用裝置,具有液晶元件、及貼於該液晶元件的雙面之偏光板等光學薄膜。該液晶元件是將厚度約1mm程度之兩枚玻璃基板隔開數微米之間隙來配置,並在該間隙內填充液晶後密封而成,其中,該玻璃基板表面上形成有透明電極、像素圖案等。 As a representative image display device equipped with a panel for image display, for example, a liquid crystal display device can be mentioned. The liquid crystal display device includes an optical film such as a liquid crystal element and a polarizing plate attached to both surfaces of the liquid crystal element. The liquid crystal element is disposed by separating two glass substrates having a thickness of about 1 mm by a gap of several micrometers, and sealing the liquid crystal in the gap, and a transparent electrode, a pixel pattern, and the like are formed on the surface of the liquid crystal substrate. .
因上述液晶顯示用面板很薄,容易受損,故特別是在行動電話、遊戲機、數位相機、車用配備等之中,一般常用的液晶顯示裝置具有在上述液晶顯示用面板的前面隔開一定空間而設有透明前面板(保護面板)的結構。 Since the above-mentioned liquid crystal display panel is thin and easily damaged, in general, in a mobile phone, a game machine, a digital camera, a car device, etc., a commonly used liquid crystal display device is provided in front of the liquid crystal display panel. A space with a transparent front panel (protective panel).
並且,近年來,在行動電話、遊戲機、數位相機、車用配備、筆記型電腦、桌上型電腦、電腦螢幕等的影像顯 示用裝置中,逐漸配備有觸控面板。這種配備有觸控面板之影像顯示用裝置,成為保護面板、觸控面板、影像顯示元件之積層結構,而在保護面板與觸控面板之間、及觸控面板與影像顯示元件之間存在空氣。 And, in recent years, video display in mobile phones, game consoles, digital cameras, car equipment, notebook computers, desktop computers, computer screens, etc. The display device is gradually equipped with a touch panel. The image display device equipped with the touch panel is a laminated structure of the protection panel, the touch panel, and the image display component, and exists between the protection panel and the touch panel, and between the touch panel and the image display component. air.
這些空間內存在之空氣成為光散射的原因,並成為對比、亮度及透光率、畫面殘影導致畫質降低的重要原因。 The air present in these spaces becomes the cause of light scattering, and becomes an important cause of contrast, brightness and light transmittance, and image degradation caused by image sticking.
為了防止這樣的危害,提案有在上述空間部分,填埋樹脂等填充物來代替空氣(可參考例如專利文獻1~4)。然而,關於專利文獻1~4所提案之填充物填埋空間部分,會有以下問題。 In order to prevent such a hazard, it is proposed to replace the air with a filler such as a resin in the space portion (see, for example, Patent Documents 1 to 4). However, the filler landfill portion proposed in Patent Documents 1 to 4 has the following problems.
亦即,專利文獻1所使用的油,防止其滲漏的密封較困難、有可能腐蝕液晶面板所用之材料。又,有保護面板破裂時油會漏出等之問題。 That is, the oil used in Patent Document 1 is difficult to prevent leakage of the seal, and may corrode the material used for the liquid crystal panel. In addition, there is a problem that the oil leaks when the protective panel is broken.
專利文獻2所使用的不飽和聚酯,容易變色成黃色而不適用於液晶顯示用裝置。 The unsaturated polyester used in Patent Document 2 is easily discolored into yellow and is not suitable for use in a liquid crystal display device.
專利文獻3所使用的矽氧烷(silicone),因其密著力小,為了固定而需要額外黏著劑,故製程變得繁雜,並且與黏著劑的黏著力不大,而有施加撞擊時會剝離使氣泡進入這樣的問題。 The silicone used in Patent Document 3 has a small adhesion force and requires an additional adhesive for fixing, so that the process becomes complicated and the adhesion to the adhesive is not large, and peeling occurs when an impact is applied. Make bubbles enter such a problem.
專利文獻4所使用的丙烯酸單體之聚合物,其黏著力小,若在小型機器則不需要額外黏著劑,但為了支撐大型液晶顯示用裝置的前面板則需要額外黏著劑,使製程變得繁雜。又,原料只使用單體而成,故黏度低、硬化時收縮較大,故會發生難以平均地製作大面積薄膜這樣的問題。 The polymer of the acrylic monomer used in Patent Document 4 has a small adhesive force, and does not require an additional adhesive in a small machine, but an additional adhesive is required to support the front panel of the large liquid crystal display device, so that the process becomes Complex. Further, since the raw material is formed using only a single monomer, the viscosity is low and the shrinkage during curing is large, so that it is difficult to produce a large-area film on average.
又,作為填埋於影像顯示用裝置的上述空間(例如,保護面板與影像顯示元件之間、保護面板與觸控面板之間、及觸控面板與影像顯示元件之間的空間)之樹脂組成物,使用熱硬化性樹脂組成物的情況,會受到作為影像顯示用裝置之構成部件的耐熱溫度的限制。 Further, as a resin composition which is buried in the space of the image display device (for example, between the protective panel and the image display element, between the protective panel and the touch panel, and between the touch panel and the image display element) When a thermosetting resin composition is used, it is limited by the heat resistance temperature of the constituent members of the image display device.
因此,作為填埋於影像顯示用裝置的該空間之樹脂組成物,有研究使用光硬化性樹脂組成物。 Therefore, as a resin composition filled in the space of the image display device, a photocurable resin composition has been studied.
專利文獻1:日本特開平05-011239號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 05-011239
專利文獻2:日本特開平03-204616號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. 03-204616
專利文獻3:日本特開平06-059253號公報 Patent Document 3: Japanese Laid-Open Patent Publication No. 06-059253
專利文獻4:日本特開2004-125868號公報 Patent Document 4: Japanese Laid-Open Patent Publication No. 2004-125868
此外,在影像顯示用裝置中,以提高顯示影像的對比等為目的,一般沿著保護面板的外周邊設置有規定寬度之框狀遮光部(例如,第1圖及第2圖表示一種影像顯示用裝置之液晶顯示用裝置1A、1B,該等裝置具備設有遮光部41之保護面板40)。該遮光部,具有遮蔽影像顯示用面板周邊部之不必要光、防止漏光導致顯示品質降低的功能。 Further, in the image display device, for the purpose of improving the contrast of the display image, a frame-shaped light blocking portion having a predetermined width is generally provided along the outer periphery of the protective panel (for example, FIGS. 1 and 2 show an image display). The liquid crystal display devices 1A and 1B of the device are provided with a protective panel 40) provided with a light shielding portion 41. The light shielding portion has a function of shielding unnecessary light in the peripheral portion of the image display panel and preventing light leakage from deteriorating in display quality.
然而,在保護面板設有遮光部之影像顯示用裝置中,上述空間內填充光硬化性樹脂組成物的情況,對於該遮 光部的背側部分之陰影部(相當於第1圖及第2圖的P部分,以下亦稱「陰影部」)的空間內所填充之光硬化性樹脂組成物,會產生充分的光無法到達、妨礙硬化等問題。 However, in the image display device in which the protective panel is provided with the light shielding portion, when the space is filled with the photocurable resin composition, the cover is filled with the photocurable resin composition. The photocurable resin composition filled in the space of the shadow portion of the back side of the light portion (corresponding to the P portion of the first and second figures, hereinafter also referred to as "shaded portion") may generate sufficient light. Reach, hinder hardening and other issues.
例如,先將保護面板配置在影像顯示元件(在其框體上組裝有液晶顯示用面板)上,然後在這些構件之間填充光硬化性樹脂組成物,若自保護面板側照射光線,則光線會透過比保護面板的框體(遮光部)更靠內側的部分(相當於第1圖和第2圖的符號Q的部分,以下也稱為「透光部」),但是,在框體(遮光部)的背側部分所填充的光硬化性樹脂組成物,光線無法充分地照射,而有無法充分地進行硬化的可能性。 For example, the protective panel is placed on the image display element (the liquid crystal display panel is assembled on the frame), and then the photocurable resin composition is filled between the members, and when the light is irradiated from the protective panel side, the light is applied. It passes through the inner side of the frame (light-shielding part) of the protective panel (corresponding to the part of the symbol Q of the first figure and the second figure, hereinafter also referred to as "light-transmitting part"), but in the frame ( In the photocurable resin composition filled in the back side portion of the light-shielding portion, light is not sufficiently irradiated, and there is a possibility that the light cannot be sufficiently cured.
若樹脂組成物的硬化不夠充分,則會大幅損害影像顯示用裝置的品質,成為信賴性降低的重大原因。 If the hardening of the resin composition is insufficient, the quality of the image display device is greatly impaired, which is a major cause of the decrease in reliability.
本發明之目的是提供一種光硬化性樹脂組成物、使用該樹脂組成物之影像顯示用裝置及該影像顯示用裝置之製造方法,該樹脂組成物具有優異硬化性,即使只有透光部曝光,在遮光部的背側部分的陰影部亦可充分進行硬化(以下亦稱「在遮光部中的硬化性」),同時具有適當黏度,且相溶性良好。 An object of the present invention is to provide a photocurable resin composition, an image display device using the resin composition, and a method for producing the image display device, wherein the resin composition has excellent curability, and even if only the light transmitting portion is exposed, The shaded portion of the back side portion of the light-shielding portion can also be sufficiently cured (hereinafter also referred to as "hardenability in the light-shielding portion"), and has an appropriate viscosity and good compatibility.
本發明人發現含有特定成分之光硬化性樹脂組成物,可解決上述問題,進而完成本發明。 The present inventors have found that a photocurable resin composition containing a specific component can solve the above problems and further complete the present invention.
亦即,本發明提供下述〔1〕~〔7〕。 That is, the present invention provides the following [1] to [7].
〔1〕一種光硬化性樹脂組成物,其含有:(A)具有源自聚丁二烯的結構單元之化合物;
(B)以下述通式(1)所表示的化合物;(C)具有以下述通式(II)所表示的基之硫醇化合物;及,(D)光聚合起始劑;其中,作為(A)成分,包含(A1)成分,該(A1)成分是具有(甲基)丙烯醯基且具有源自聚丁二烯的結構單元之化合物;
(通式(1)中,R1表示氫原子或甲基,R2表示氫原子或碳數1~12的烷基,n表示1~7的整數);
(通式(II)中的R3及R4,各自獨立地表示氫原子或碳數1~5的烷基,q表示0~3的整數,*表示鍵結部分)。 (R 3 and R 4 in the formula (II) each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, q represents an integer of 0 to 3, and * represents a bonding moiety).
〔2〕如上述〔1〕所述之光硬化性樹脂組成物,其中,(C)成分是以下述通式(2)所表示的硫醇化合物,
(通式(2)中的R3及R4,各自獨立地表示氫原子或碳數1~5的烷基,p表示1~6的整數,q表示0~3的整數,A 表示p價的有機基)。 (R 3 and R 4 in the formula (2) each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, p represents an integer of 1 to 6, q represents an integer of 0 to 3, and A represents a p-valent value. Organic base).
〔3〕如上述〔1〕或〔2〕所述之光硬化性樹脂組成物,其中,前述通式(1)中的R2是碳數4~12的烷基。 [3] The photocurable resin composition according to the above [1], wherein R 2 in the above formula (1) is an alkyl group having 4 to 12 carbon atoms.
〔4〕如上述〔1〕~〔3〕中的任一項所述之光硬化性樹脂組成物,其實質上不含有機溶劑,且在25℃時的黏度為500~5000mPa.s。 [4] The photocurable resin composition according to any one of the above [1] to [3], which substantially does not contain an organic solvent, and has a viscosity at 25 ° C of 500 to 5000 mPa. s.
〔5〕如上述〔1〕~〔4〕中的任一項所述之光硬化性樹脂組成物,其中,(C)成分的含量,相對於(A)~(C)成分的總量,為3~30質量%。 [5] The photocurable resin composition according to any one of the above [1], wherein the content of the component (C) is based on the total amount of the components (A) to (C). It is 3 to 30% by mass.
〔6〕如上述〔1〕~〔5〕中的任一項所述之光硬化性樹脂組成物,其中,(A1)成分的含量,相對於(A)成分的總量,為25~100質量%。 [6] The photocurable resin composition according to any one of the above [1], wherein the content of the component (A1) is 25 to 100 with respect to the total amount of the component (A). quality%.
〔7〕如上述〔1〕~〔6〕中的任一項所述之光硬化性樹脂組成物,其中,作為(A)成分,進一步包含(A2)成分,該(A2)成分是不具有(甲基)丙烯醯基且具有源自聚丁二烯的結構單元之化合物。 The photocurable resin composition according to any one of the above [1], wherein the component (A) further contains the component (A2), and the component (A2) does not have A (meth)acrylonitrile group having a compound derived from a structural unit of polybutadiene.
〔8〕如上述〔7〕所述之光硬化性樹脂組成物,其中,(A1)成分與(A2)的質量比〔(A1)/(A2)〕為25/75~95/5。 [8] The photocurable resin composition according to the above [7], wherein the mass ratio of (A1) component to (A2) [(A1)/(A2)] is 25/75 to 95/5.
〔9〕如上述〔2〕~〔8〕中的任一項所述之光硬化性樹脂組成物,其中,前述通式(2)中的A,是以下述式(C-1)或(C-2)所表示的基、或是碳數1~12的伸烷基,
(式(C-1)或(C-2)中,*表示鍵結部分,X1~X7各自獨立地表示單鍵、或可具有取代基之碳數1~12的伸烷基)。 (In the formula (C-1) or (C-2), * represents a bonding moiety, and X 1 to X 7 each independently represent a single bond or an alkylene group having 1 to 12 carbon atoms which may have a substituent).
〔10〕如上述〔1〕~〔9〕中的任一項所述之光硬化性樹脂組成物,其中,(B)成分的含量,相對於(A)~(C)成分的總量,為1~40質量%。 [10] The photocurable resin composition according to any one of the above [1], wherein the content of the component (B) is based on the total amount of the components (A) to (C). It is 1 to 40% by mass.
〔11〕如上述〔1〕~〔10〕中的任一項所述之光硬化性樹脂組成物,其中,(A)成分的含量,相對於(A)~(C)成分的總量,為50~98質量%。 [11] The photocurable resin composition according to any one of the above [1], wherein the content of the component (A) is based on the total amount of the components (A) to (C). It is 50 to 98% by mass.
〔12〕一種影像顯示用裝置,是具有積層結構之影像顯示用裝置,該積層結構包含:影像顯示元件,其具有影像顯示部;保護面板,其具有沿著外周邊的遮光部;及,樹脂層,其存在於前述影像顯示元件與前述保護面板之間;其中,前述樹脂層是如上述〔1〕~〔11〕中的任一項所述之光硬化性樹脂組成物的硬化物。 [12] An image display device comprising a laminated structure, comprising: an image display device having an image display portion; a protective panel having a light shielding portion along an outer periphery; and a resin The layer is a cured product of the photocurable resin composition according to any one of the above [1] to [11], wherein the resin layer is present between the image display element and the protective panel.
〔13〕一種影像顯示用裝置,是具有積層結構之影像顯 示用裝置,該積層結構包含:影像顯示元件,其具有影像顯示部;觸控面板;保護面板,其具有沿著外周邊的遮光部;及,樹脂層,其存在於前述觸控面板與前述保護面板之間;其中,前述樹脂層是如上述〔1〕~〔11〕中的任一項所述之光硬化性樹脂組成物的硬化物。 [13] A device for image display, which is an image display having a laminated structure The display device includes: an image display element having an image display portion; a touch panel; a protection panel having a light shielding portion along the outer periphery; and a resin layer present on the touch panel and the foregoing The cured resin is a cured product of the photocurable resin composition according to any one of the above [1] to [11].
〔14〕一種影像顯示用裝置的製造方法,是先將具有影像顯示部之影像顯示元件或觸控面板,與具有沿著外周邊的遮光部之保護面板對向配置,然後使光硬化性樹脂組成物介於這些構件的間隙中,並使該光硬化性樹脂組成物硬化,來製造影像顯示用裝置的方法, [14] A method of manufacturing an image display device, wherein an image display element or a touch panel having a video display unit is disposed opposite to a protective panel having a light shielding portion along an outer periphery, and then a photocurable resin is disposed. a method in which a composition is interposed between the members and the photocurable resin composition is cured to produce an image display device.
其中,使如上述〔1〕~〔11〕中的任一項所述之光硬化性樹脂組成物介於前述間隙中,並至少自前述保護面板側進行光照射來使該光硬化性樹脂組成物硬化。 In the above-mentioned gap, the photocurable resin composition according to any one of the above [1] to [11] is light-irradiated from at least the protective panel side to form the photocurable resin. Hardening of matter.
本發明之光硬化性樹脂組成物,其在遮光部中的硬化性優異,具有適當黏度,且相溶性良好。又,光硬化性樹脂組成物的硬化物,其透明性及折射率優異,具有適當的介電係數。 The photocurable resin composition of the present invention is excellent in curability in a light-shielding portion, has an appropriate viscosity, and has good compatibility. Further, the cured product of the photocurable resin composition is excellent in transparency and refractive index, and has an appropriate dielectric constant.
1A、1B‧‧‧液晶顯示用裝置 1A, 1B‧‧‧ liquid crystal display device
1‧‧‧影像顯示元件 1‧‧‧Image display components
10‧‧‧液晶顯示單元 10‧‧‧LCD unit
20、22‧‧‧偏光板 20, 22‧‧‧ polarizing plate
30‧‧‧觸控面板 30‧‧‧Touch panel
31、32‧‧‧樹脂層 31, 32‧‧‧ resin layer
40‧‧‧保護面板 40‧‧‧Protection panel
41‧‧‧遮光部 41‧‧‧Lighting Department
50‧‧‧背光系統 50‧‧‧Backlight system
P‧‧‧遮光部的背側部分 P‧‧‧Back side of the sunscreen
Q‧‧‧透光部 Q‧‧‧Transmission Department
第1圖是示意性地表示本發明之影像顯示用裝置的一例也就是液晶顯示裝置的一實施形態的側面剖面圖。 Fig. 1 is a side cross-sectional view schematically showing an embodiment of a liquid crystal display device which is an example of the image display device of the present invention.
第2圖是示意性地表示本發明之影像顯示用裝置的一例 也就是液晶顯示裝置的一實施形態,亦即示意性地表示配備有觸控面板之液晶顯示裝置的側面剖面圖。 Fig. 2 is a view schematically showing an example of the image display device of the present invention That is, an embodiment of the liquid crystal display device, that is, a side cross-sectional view schematically showing a liquid crystal display device equipped with a touch panel.
以下,藉由實施形態,更詳細地說明本發明之光硬化性樹脂組成物、使用該樹脂組成物之影像顯示用裝置的製造方法、以及影像顯示用裝置。此外,本發明並未限定於該實施形態。 Hereinafter, the photocurable resin composition of the present invention, the method for producing an image display device using the resin composition, and the image display device will be described in more detail by way of embodiments. Further, the present invention is not limited to the embodiment.
本說明書中「(甲基)丙烯酸酯」為「丙烯酸酯」及其對應之「甲基丙烯酸酯」,同樣地「(甲基)丙烯酸樹脂」為「丙烯酸樹脂」及其對應之「甲基丙烯酸樹脂」,「(甲基)丙烯醯基」為「丙烯醯基」及其對應之「甲基丙烯醯基」。 In the present specification, "(meth)acrylate" is "acrylate" and its corresponding "methacrylate", and similarly, "(meth)acrylic resin" is "acrylic resin" and its corresponding "methacrylic acid" "Resin", "(meth)acrylonitrile" is "acryloyl" and its corresponding "methacryl".
本發明之光硬化性樹脂組成物(以下亦僅稱「樹脂組成物」),其含有(A)具有源自聚丁二烯的結構單元之化合物、(B)以通式(1)所表示的化合物、(C)具有以通式(2)所表示的基之硫醇化合物、及(D)光聚合起始劑,其中,作為(A)成分,包含(A1)成分,該(A1)成分是具有(甲基)丙烯醯基且具有源自聚丁二烯的結構單元之化合物。以下詳細說明各成分。 The photocurable resin composition of the present invention (hereinafter also referred to simply as "resin composition") contains (A) a compound having a structural unit derived from polybutadiene, and (B) represented by the formula (1) The compound (C) has a thiol compound represented by the formula (2), and (D) a photopolymerization initiator, wherein the component (A) contains the component (A1), and the component (A1) The component is a compound having a (meth)acrylonitrile group and having a structural unit derived from polybutadiene. Each component will be described in detail below.
<(A)成分:具有源自聚丁二烯的結構單元之化合物> <(A) component: a compound having a structural unit derived from polybutadiene>
本發明之樹脂組成物,含有具有源自聚丁二烯的結構單元之化合物作為(A)成分。 The resin composition of the present invention contains a compound having a structural unit derived from polybutadiene as the component (A).
(A)成分被區分為(A1)成分及(A2)成分,(A1) 成分是具有(甲基)丙烯醯基且具有源自聚丁二烯的結構單元之化合物(以下亦稱「聚丁二烯(甲基)丙烯酸酯」);(A2)成分是不具有(甲基)丙烯醯基但具有源自聚丁二烯的結構單元之化合物,本發明之樹脂組成物含有作為(A1)成分之聚丁二烯(甲基)丙烯酸酯。 (A) component is classified into (A1) component and (A2) component, (A1) The component is a compound having a (meth)acryl fluorenyl group and having a structural unit derived from polybutadiene (hereinafter also referred to as "polybutadiene (meth) acrylate"); (A2) component is not possessed (A) A compound having a propylene group but having a structural unit derived from polybutadiene, and the resin composition of the present invention contains a polybutadiene (meth) acrylate as the component (A1).
由提高所得到的樹脂組成物的在遮光部中的硬化性的觀點,(A1)成分的含量,相對於(A)成分的總量,較佳為25質量%以上,更佳為30質量%以上,進一步較佳為40質量%以上,更佳為52質量%以上。 The content of the component (A1) is preferably 25% by mass or more, and more preferably 30% by mass based on the total amount of the component (A), from the viewpoint of improving the curability in the light-shielding portion of the obtained resin composition. The above is more preferably 40% by mass or more, and still more preferably 52% by mass or more.
((A1)成分:具有(甲基)丙烯醯基且具有源自聚丁二烯的結構單元之化合物) (Component (A1): a compound having a (meth)acryl fluorenyl group and having a structural unit derived from polybutadiene)
作為(A1)成分之具有(甲基)丙烯醯基且具有源自聚丁二烯的結構單元之化合物,可舉例如使聚丁二烯二醇與具有(甲基)丙烯醯基之單異氰酸酯化合物反應所得之化合物。 The compound having a (meth) acrylonitrile group and having a structural unit derived from polybutadiene as the component (A1) may, for example, be a polybutadiene diol and a monoisocyanate having a (meth) acrylonitrile group. The compound obtained by the reaction of the compound.
上述聚丁二烯中,有具有「1,4-結構單元」或「1,2-結構單元」之物。在此,聚丁二烯之「1,4-結構單元」是以下述化學式(1t)或(1c)表示之結構單元,「1,2-結構單元」是以下述化學式(1d)表示之重複單元。 Among the above polybutadienes, there are those having "1,4-structural unit" or "1,2-structural unit". Here, the "1,4-structural unit" of the polybutadiene is a structural unit represented by the following chemical formula (1t) or (1c), and the "1,2-structural unit" is a repeat represented by the following chemical formula (1d) unit.
作為主要具有1,4-結構單元之聚丁二烯二醇,可舉例如Poly bd R-45HT、Poly bd R-15HT(1,4-結構單元的含量比例:80%,出光興產公司製,商品名)。 The polybutadiene diol having a main 1,4-structural unit may, for example, be Poly bd R-45HT or Poly bd R-15HT (content ratio of 1,4-structural unit: 80%, manufactured by Idemitsu Kosan Co., Ltd.) ,Product name).
作為主要具有1,2-結構單元之聚丁二烯二醇,有例示如下述通式(1a)所表示之化合物,具體而言,可舉例如G-1000(1,2-結構單元的含量比例:85%)、G-2000(1,2-結構單元的含量比例:90%)(以上為商品名,日本曹達(股)製)。 The polybutadiene diol having a 1,2-structural unit is exemplified by a compound represented by the following formula (1a), and specifically, for example, G-1000 (1,2-structural unit content) Ratio: 85%), G-2000 (content ratio of 1,2-structural unit: 90%) (The above is the trade name, manufactured by Japan Soda Co., Ltd.).
(式(1a)中,n1為1~60的整數) (In the formula (1a), n1 is an integer from 1 to 60)
(A1)成分中,作為1,2-結構單元與1,4-結構單元的含量比例〔1,2-結構單元/1,4-結構單元〕,較佳為10/90~98/2,更佳為60/40~98/2,進一步較佳為 70/30~97/3,更佳為80/20~95/5。 In the component (A1), the content ratio of the 1,2-structural unit to the 1,4-structural unit [1,2-structural unit/1,4-structural unit] is preferably 10/90 to 98/2. More preferably 60/40~98/2, further preferably 70/30~97/3, more preferably 80/20~95/5.
作為前述具有(甲基)丙烯醯基之單異氰酸酯化合物,可舉例如2-異氰酸基乙基(甲基)丙烯酸酯、2-異氰酸基丙基(甲基)丙烯酸酯、3-異氰酸基丙基(甲基)丙烯酸酯等。 Examples of the monoisocyanate compound having a (meth)acryl fluorenyl group include 2-isocyanatoethyl (meth) acrylate, 2-isocyanatopropyl (meth) acrylate, and 3- Isocyanatopropyl (meth) acrylate or the like.
此外,聚丁二烯二醇與具有(甲基)丙烯醯基之單異氰酸酯化合物的反應,可例如在對甲氧基酚等之聚合抑制劑及二月桂酸二丁基錫等之觸媒存在下進行。 Further, the reaction of the polybutadiene diol with a monoisocyanate compound having a (meth) acrylonitrile group can be carried out, for example, in the presence of a polymerization inhibitor such as p-methoxyphenol or a catalyst such as dibutyltin dilaurate. .
本發明中,(A1)成分的重量平均分子量(Mw),由硬化性、可撓性及操作性等觀點而言,較佳為1,000~30,000,更佳為2,000~20,000,進一步較佳為3,000~10,000。 In the present invention, the weight average molecular weight (Mw) of the component (A1) is preferably from 1,000 to 30,000, more preferably from 2,000 to 20,000, still more preferably from 3,000 to 20,000, from the viewpoints of hardenability, flexibility, and workability. ~10,000.
此外,本說明書中,(A)成分的重量平均分子量(Mw),是經由膠體滲透層析(GPC)測定,使用標準聚苯乙烯檢量線換算而得之值。又,數量平均分子量、重量平均分子量及分散度,是(A)成分中,分子量Mi之分子存在有Ni個時,如下述定義。 Further, in the present specification, the weight average molecular weight (Mw) of the component (A) is a value obtained by conversion by a colloidal permeation chromatography (GPC) using a standard polystyrene calibration line. Further, the number average molecular weight, the weight average molecular weight, and the degree of dispersion are defined as follows when the number of molecules having the molecular weight Mi is Ni in the component (A).
(a)數量平均分子量(Mn) (a) number average molecular weight (Mn)
Mn=Σ(NiMi)/Σ Ni=Σ XiMi(Xi=分子量Mi之分子的莫耳分率=Ni/Σ Ni) Mn=Σ(N i M i )/Σ Ni=Σ X i M i (X i = mole fraction of the molecule of molecular weight M i = N i /Σ N i )
(b)重量平均分子量(Mw) (b) Weight average molecular weight (Mw)
Mw=Σ(NiMi 2)/Σ NiMi=Σ WiMi(Wi=分子量Mi之分子的重量分率=NiMi/Σ NiMi) Mw=Σ(N i M i 2 )/Σ NiM i =Σ W i M i (W i = weight fraction of molecules of molecular weight M i = N i M i /Σ N i M i )
(c)分子量分布(分散度) (c) Molecular weight distribution (dispersion)
分散度=Mw/Mn Dispersion = Mw / Mn
(A1)成分的含量,由提高在遮光部中的硬化性的觀點而言,相對於(A)成分的總量,較佳為25~100質量%,更佳為30~100質量%,進一步較佳為40~100質量%,更佳為45~100質量%。 The content of the component (A1) is preferably from 25 to 100% by mass, more preferably from 30 to 100% by mass, based on the total amount of the component (A), from the viewpoint of improving the curability in the light-shielding portion. It is preferably 40 to 100% by mass, more preferably 45 to 100% by mass.
((A2)成分:不具有(甲基)丙烯醯基且具有源自聚丁二烯的結構單元之化合物) (Component (A2): a compound having no (meth)acryl fluorenyl group and having a structural unit derived from polybutadiene)
本發明之樹脂組成物中,可由只含有(A1)成分之物作為(A)成分,但是,由硬化性、硬化收縮率及操作性的觀點,作為(A)成分,較佳為同時含有(A1)及(A2)不具有(甲基)丙烯醯基且具有源自聚丁二烯的結構單元之化合物(以下亦稱「(A2)成分」)。 In the resin composition of the present invention, the component (A1) may be contained as the component (A). However, from the viewpoint of curability, curing shrinkage ratio, and handleability, the component (A) preferably contains ( A1) and (A2) are compounds having a (meth)acrylonitrile group and having a structural unit derived from polybutadiene (hereinafter also referred to as "(A2) component").
作為(A2)成分之化合物,可舉例如聚丁二烯二醇、聚丁二烯二羧酸、馬來酸化聚丁二烯、丁二烯均聚物、可與丁二烯共聚之共聚物、使聚丁二烯二醇與具有異氰酸酯基之化合物反應所得之化合物、使聚丁二烯二醇與具有羧基之化合物反應所得之化合物、使聚丁二烯二羧酸與具有羥基之化合物反應所得之化合物、使聚丁二烯二羧酸與具有環氧基之化合物反應所得之化合物等。 The compound of the component (A2) may, for example, be a polybutadiene diol, a polybutadiene dicarboxylic acid, a maleated polybutadiene, a butadiene homopolymer, or a copolymer copolymerizable with butadiene. a compound obtained by reacting a polybutadiene diol with a compound having an isocyanate group, a compound obtained by reacting a polybutadiene diol with a compound having a carboxyl group, and reacting a polybutadiene dicarboxylic acid with a compound having a hydroxyl group The obtained compound, a compound obtained by reacting a polybutadiene dicarboxylic acid with a compound having an epoxy group, and the like.
作為主要具有1,2-結構單元之聚丁二烯二羧酸,可舉例如C-1000(1,2-結構單元的含量比例:85%以上,日本曹達(股)製,商品名)。 The polybutadiene dicarboxylic acid which has a 1,2- structural unit, for example, C-1000 (content ratio of a 1,2- structural unit: 85% or more, manufactured by Nippon Soda Co., Ltd., trade name).
作為主要具有1,2-結構單元之聚丁二烯均聚物,可舉例如B-1000(1,2-結構單元的含量比例:85%)、B-2000 (1,2-結構單元的含量比例:85%)、B-3000(1,2-結構單元的含量比例:90%)(以上為商品名,日本曹達(股)製)。 As a polybutadiene homopolymer mainly having a 1,2-structural unit, for example, B-1000 (content ratio of 1,2-structural unit: 85%), B-2000 (1,2-content unit content ratio: 85%), B-3000 (1,2-structural unit content ratio: 90%) (the above is a trade name, manufactured by Japan Soda Co., Ltd.).
作為上述使聚丁二烯二醇與具有異氰酸酯基之化合物反應所得之化合物,可舉例如TEA-1000、TE-2000(日本曹達(股)製,商品名)。 The compound obtained by reacting the polybutadiene diol with the compound having an isocyanate group may, for example, be TEA-1000 or TE-2000 (manufactured by Nippon Soda Co., Ltd., trade name).
作為上述使聚丁二烯二羧酸與具有環氧基之化合物反應所得之化合物,可舉例如EPB13(日本曹達(股)製,商品名)。 The compound obtained by reacting the polybutadiene dicarboxylic acid with a compound having an epoxy group is, for example, EPB13 (product name: manufactured by Nippon Soda Co., Ltd.).
(A1)成分與(A2)的質量比〔(A1)/(A2)〕,由提高在遮光部中的硬化性的觀點而言,與得到具有適當黏度之樹脂組成物的觀點而言,較佳為25/75~95/5,更佳為30/70~90/10,進一步較佳為40/60~80/20,更佳為45/55~70/30。 The mass ratio of (A1) component to (A2) [(A1)/(A2)] is improved from the viewpoint of improving the curability in the light-shielding portion, and from the viewpoint of obtaining a resin composition having an appropriate viscosity. The ratio is preferably 25/75 to 95/5, more preferably 30/70 to 90/10, further preferably 40/60 to 80/20, more preferably 45/55 to 70/30.
若該質量比為25/75以上,則能提高所得到的樹脂組成物的在遮光部中的硬化性。另一方面,若該質量比為95/5以下,則能作成具有適當的黏度的樹脂組成物。 When the mass ratio is 25/75 or more, the curability of the obtained resin composition in the light shielding portion can be improved. On the other hand, when the mass ratio is 95/5 or less, a resin composition having an appropriate viscosity can be obtained.
本發明之樹脂組成物中(A)成份的含量,相對於(A)~(C)成分的總量,較佳為50~98質量%,更佳為60~94質量%,進一步較佳為68~92質量%,更佳為80~92質量%。 The content of the component (A) in the resin composition of the present invention is preferably from 50 to 98% by mass, more preferably from 60 to 94% by mass, based on the total amount of the components (A) to (C), further preferably 68 to 92% by mass, more preferably 80 to 92% by mass.
(A)成份的含量若在50質量%以上,則可提高所得到的樹脂組成物在遮光部中的硬化性,且降低介電常數。另一方面,若在98質量%以下,則可確保(B)成分及(C)成分 的含量,故可作為具有適當黏度的樹脂組成物,同時提高樹脂組成物的硬化物之透明性。 When the content of the component (A) is at least 50% by mass, the curability of the obtained resin composition in the light-shielding portion can be improved, and the dielectric constant can be lowered. On the other hand, when it is 98% by mass or less, the component (B) and the component (C) can be secured. The content is such that it can be used as a resin composition having an appropriate viscosity while improving the transparency of the cured product of the resin composition.
<(B)成分:通式(1)所表示的化合物> <(B) component: a compound represented by the formula (1)>
本發明之樹脂組成物,含有下述通式(1)所表示的化合物作為(B)成分。 The resin composition of the present invention contains a compound represented by the following formula (1) as the component (B).
上述通式(1)中,R1表示氫原子或甲基。 In the above formula (1), R 1 represents a hydrogen atom or a methyl group.
又,上述通式(1)中的R2表示氫原子或碳數1~12的烷基。該烷基的碳數若超過12,則與(A)成分之相溶性會惡化,降低硬化物的透明性故不佳。 Further, R 2 in the above formula (1) represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. When the carbon number of the alkyl group exceeds 12, the compatibility with the component (A) is deteriorated, and the transparency of the cured product is lowered, which is not preferable.
因此,作為R2,由使與(A)成分之相溶性良好,同時使所得到的樹脂組成物在遮光部中的硬化性良好的觀點而言,較佳為碳數4~12的烷基,更佳為碳數5~11的烷基,進一步較佳為碳數6~10的烷基。 Therefore, R 2 is preferably an alkyl group having 4 to 12 carbon atoms from the viewpoint of improving the compatibility with the component (A) and improving the curability of the obtained resin composition in the light-shielding portion. More preferably, it is an alkyl group having 5 to 11 carbon atoms, and further preferably an alkyl group having 6 to 10 carbon atoms.
作為碳數1~12的烷基,可舉例如甲基、乙基、丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基、十二基等。 Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, and a hexylene group. Base, octyl, decyl, fluorenyl, eleven, twelfth, etc.
此外,上述烷基可為直鏈或支鏈狀之任一種。 Further, the above alkyl group may be either linear or branched.
又,這些烷基的氫原子之至少一部分,亦可被例如羥基、鹵素原子、烷基、環烷基、芳基、芳烷基、羰基、醛基、酯基、醯胺基、烷氧基、芳氧基、烷硫基、芳硫基、胺基、矽 基、矽氧基(silyloxy)等取代。 Further, at least a part of the hydrogen atoms of these alkyl groups may be, for example, a hydroxyl group, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, a carbonyl group, an aldehyde group, an ester group, a decylamino group or an alkoxy group. , aryloxy, alkylthio, arylthio, amine, hydrazine Substituted by a group, a silyloxy group or the like.
上述通式(1)中的n表示1~7的整數,而由(A)成分與(C)成分之相溶性的觀點而言,較佳為1~6,更佳為1~5,進一步較佳為3~5。 n in the above formula (1) represents an integer of 1 to 7, and is preferably from 1 to 6, more preferably from 1 to 5, from the viewpoint of compatibility between the component (A) and the component (C). It is preferably 3 to 5.
n若超過7,則(A)成分與(C)成分之相溶性降低,有使硬化物的透明性降低之傾向。又,所得之樹脂組成物的遮光物之硬化性會降低故不佳。 When n exceeds 7, the compatibility of the component (A) and the component (C) is lowered, and the transparency of the cured product tends to be lowered. Moreover, the hardenability of the shade of the obtained resin composition is lowered, which is not preferable.
另外,本發明中,n代表通式(1)所表示之化合物的環氧乙烷鏈之數量平均值。 Further, in the present invention, n represents the average value of the number of ethylene oxide chains of the compound represented by the general formula (1).
作為上述通式(1)所表示的化合物,可舉例如苯氧基乙基(甲基)丙烯酸酯、丁基苯氧基聚乙二醇(甲基)丙烯酸酯、戊基苯氧基聚乙二醇(甲基)丙烯酸酯、己基苯氧基聚乙二醇(甲基)丙烯酸酯、庚基苯氧基聚乙二醇(甲基)丙烯酸酯、辛基苯氧基聚乙二醇(甲基)丙烯酸酯、壬基苯氧基聚乙二醇(甲基)丙烯酸酯、癸基苯氧基聚乙二醇(甲基)丙烯酸酯等。 The compound represented by the above formula (1) may, for example, be phenoxyethyl (meth) acrylate, butyl phenoxy polyethylene glycol (meth) acrylate or pentyl phenoxy poly ethane. Glycol (meth) acrylate, hexyl phenoxy polyethylene glycol (meth) acrylate, heptyl phenoxy polyethylene glycol (meth) acrylate, octyl phenoxy polyethylene glycol ( Methyl) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, and the like.
這些化合物可單獨或組合兩種以上使用。 These compounds may be used alone or in combination of two or more.
此外,作為前述通式(1)所表示的化合物,適合的市售品可舉例如FA-310A(日立化成(股)製,商品名,通式(1)中的R1:氫原子、R2:氫原子、n的平均值:4之化合物)、FA-314A(日立化成(股)製,商品名,通式(1)中的R1:氫原子、R2:壬基、n的平均值:4之化合物)。 In addition, as a commercially available product of the above-mentioned general formula (1), for example, FA-310A (manufactured by Hitachi Chemical Co., Ltd., trade name, R 1 in the general formula (1): hydrogen atom, R 2 : hydrogen atom, average value of n: compound of 4), FA-314A (manufactured by Hitachi Chemical Co., Ltd., trade name, R 1 in the formula (1): hydrogen atom, R 2 : mercapto group, n Average: 4 compounds).
作為(B)成分的重量平均分子量(Mw),較佳為3000以下,更佳為100~2800,進一步較佳為150~2000,更 佳為200~1500。 The weight average molecular weight (Mw) of the component (B) is preferably 3,000 or less, more preferably 100 to 2,800, still more preferably 150 to 2,000, more preferably Good for 200~1500.
本發明之樹脂組成物中(B)成份的含量,相對於(A)~(C)成分的總量,較佳為1~40質量%,更佳為3~30質量%,進一步較佳為4~27質量%。 The content of the component (B) in the resin composition of the present invention is preferably from 1 to 40% by mass, more preferably from 3 to 30% by mass, based on the total amount of the components (A) to (C), further preferably 4 to 27% by mass.
(B)成分的含量若在1質量%以上,則可作成具有適當黏度之樹脂組成物,使塗佈時之操作性良好,同時降低硬化收縮率。又,使所得到的樹脂組成物在遮光部中的硬化性良好,同時提高硬化物的透明性。 When the content of the component (B) is at least 1% by mass, a resin composition having an appropriate viscosity can be obtained, and the workability at the time of coating can be improved, and the curing shrinkage ratio can be lowered. Moreover, the obtained resin composition is excellent in the hardenability in the light-shielding portion, and the transparency of the cured product is improved.
又,若在40質量%以下,則可抑制硬化收縮率升高。 Moreover, when it is 40 mass % or less, it can suppress that the hardening shrinkage rate raises.
<(B2)成分:除了前述通式(1)所表示的化合物以外之分子內具有一個乙烯性不飽和基之低分子量單體> <Component (B2): Low molecular weight monomer having one ethylenically unsaturated group in the molecule other than the compound represented by the above formula (1)>
此外,本發明之樹脂組成物中,亦可含有除了前述通式(1)所表示的化合物以外之分子內具有一個乙烯性不飽和基之低分子量單體(B2)。 Further, the resin composition of the present invention may contain a low molecular weight monomer (B2) having one ethylenically unsaturated group in the molecule other than the compound represented by the above formula (1).
作為這種低分子量單體(B2),可舉例如下述通式(3)所表示之烷基(甲基)丙烯酸酯、以及分子內具有(甲基)丙烯醯基及羥基或醚鍵之化合物。 The low molecular weight monomer (B2) may, for example, be an alkyl (meth) acrylate represented by the following formula (3), and a compound having a (meth) acryl fluorenyl group and a hydroxyl group or an ether bond in the molecule. .
上述通式(3)中,R11表示氫原子或甲基,R12表示碳數4~20之烷基。R12由賦予柔軟性的觀點而言,較佳為碳數6~18之烷基,更佳為碳數8~16之烷基。 In the above formula (3), R 11 represents a hydrogen atom or a methyl group, and R 12 represents an alkyl group having 4 to 20 carbon atoms. R 12 is preferably an alkyl group having 6 to 18 carbon atoms, more preferably an alkyl group having 8 to 16 carbon atoms, from the viewpoint of imparting flexibility.
作為上述通式(3)所表示的烷基(甲基)丙烯酸酯, 可舉例如正丁基(甲基)丙烯酸酯、第三丁基(甲基)丙烯酸酯、異丁基(甲基)丙烯酸酯、正戊基(甲基)丙烯酸酯、正辛基(甲基)丙烯酸酯、異辛基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯、異癸基(甲基)丙烯酸酯、正己基(甲基)丙烯酸酯、硬脂基(甲基)丙烯酸酯、月桂基(甲基)丙烯酸酯、十三基(甲基)丙烯酸酯等。這些化合物可單獨或組合兩種以上使用。 As the alkyl (meth) acrylate represented by the above formula (3), For example, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, n-octyl (methyl) Acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-hexyl (meth) acrylate, stearyl (a) Acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, and the like. These compounds may be used alone or in combination of two or more.
作為分子內具有(甲基)丙烯醯基及羥基或醚鍵之化合物,可舉例如2-羥基乙基(甲基)丙烯酸酯、1-羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基)丙烯酸酯、3-羥基丙基(甲基)丙烯酸酯、1-羥基丙基(甲基)丙烯酸酯、4-羥基丁基(甲基)丙烯酸酯、3-羥基丁基(甲基)丙烯酸酯、2-羥基丁基(甲基)丙烯酸酯、1-羥基丁基(甲基)丙烯酸酯等之含有羥基之(甲基)丙烯酸酯;羥基乙基(甲基)丙烯醯胺等之含有羥基之(甲基)丙烯醯胺;二乙二醇或三乙二醇等之聚乙二醇單(甲基)丙烯酸酯;二丙二醇或三丙二醇等之聚丙二醇單(甲基)丙烯酸酯;二丁二醇或三丁二醇等之聚丁二醇單(甲基)丙烯酸酯;丙烯醯基嗎啉等之含有嗎啉基之(甲基)丙烯酸酯。 Examples of the compound having a (meth)acryl fluorenyl group and a hydroxyl group or an ether bond in the molecule include 2-hydroxyethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, and 2-hydroxy propyl. Base (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxy butyl ( a hydroxyl group-containing (meth) acrylate such as methyl acrylate, 2-hydroxybutyl (meth) acrylate or 1-hydroxybutyl (meth) acrylate; hydroxyethyl (meth) propylene oxime a hydroxyl group-containing (meth) acrylamide such as an amine; a polyethylene glycol mono(meth)acrylate such as diethylene glycol or triethylene glycol; a polypropylene glycol mono(methyl) such as dipropylene glycol or tripropylene glycol. An acrylate, a polybutylene glycol mono(meth)acrylate such as dibutylene glycol or tributyl glycol; a (meth) acrylate containing a morpholinyl group such as acryloylmorpholine.
這些之中,由耐溼熱信賴性及塗佈時之操作性的觀點而言,較佳為含有羥基之(甲基)丙烯酸酯、含有嗎啉基之(甲基)丙烯酸酯,更佳為4-羥基丁基(甲基)丙烯酸酯、丙烯醯基嗎啉。 Among these, from the viewpoint of moisture-heat resistance and workability at the time of coating, a (meth) acrylate having a hydroxyl group and a (meth) acrylate containing a morpholinyl group are preferred, and more preferably 4 - Hydroxybutyl (meth) acrylate, acryl morphomorpholine.
這些低分子量單體(B2)可單獨或組合兩種以上使用。 作為這些低分子量單體(B2)的重量平均分子量(Mw),較佳為3000以下,更佳為100~2800,進一步較佳為150~2000。 These low molecular weight monomers (B2) may be used singly or in combination of two or more. The weight average molecular weight (Mw) of these low molecular weight monomers (B2) is preferably 3,000 or less, more preferably from 100 to 2,800, still more preferably from 150 to 2,000.
又,低分子量單體(B2)的含量,相對於(B)成分100質量份,較佳為0~30質量份,更佳為0~15質量份。 In addition, the content of the low molecular weight monomer (B2) is preferably 0 to 30 parts by mass, more preferably 0 to 15 parts by mass, per 100 parts by mass of the component (B).
<(C)成分:具有以通式(II)所表示的基之硫醇化合物> <(C) component: a thiol compound having a group represented by the formula (II)>
本發明之樹脂組成物,含有以下述通式(II)所表示的基之硫醇化合物作為(C)成分。此外,該化合物可單獨或組合兩種以上使用。 The resin composition of the present invention contains a thiol compound represented by the following formula (II) as the component (C). Further, the compounds may be used singly or in combination of two or more.
上述通式(II)中的R3及R4,各自獨立地表示氫原子或碳數1~5的烷基,q表示0~3的整數,*表示鍵結部分。 R 3 and R 4 in the above formula (II) each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, q represents an integer of 0 to 3, and * represents a bond moiety.
R3及R4,各自獨立地表示氫原子或碳數1~5的烷基,其中較佳為氫原子或碳數1~3之烷基,更佳為氫原子或甲基。此外,上述烷基可為直鏈或支鏈之任一種。 R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable. Further, the above alkyl group may be either a straight chain or a branched chain.
作為碳數1~5之烷基,可舉例如甲基、乙基、丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基、戊基等。 Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a second butyl group, an isobutyl group, a tert-butyl group, and a pentyl group.
通式(II)中的q,表示0~3的整數,其中較佳為1~2的整數,更佳為1。 q in the formula (II) represents an integer of 0 to 3, and preferably an integer of 1 to 2, more preferably 1.
又,具有以上述通式(II)所表示的基之硫醇化合物中,由所得之樹脂組成物的安定性的觀點而言,較佳為下述通式(2)所表示的硫醇化合物。 In addition, from the viewpoint of the stability of the obtained resin composition, the thiol compound having a group represented by the above formula (II) is preferably a thiol compound represented by the following formula (2). .
上述通式(2)中的R3及R4,各自獨立地表示氫原子或碳數1~5的烷基,其中較佳為氫原子或碳數1~3之烷基,更佳為氫原子或甲基。此外,上述烷基可為直鏈或支鏈狀之任一種。 R 3 and R 4 in the above formula (2) each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferred, and hydrogen is more preferred. Atom or methyl. Further, the above alkyl group may be either linear or branched.
通式(2)中的p表示1~6的整數,其中較佳為1~4的整數,更佳為2~4的整數。 p in the general formula (2) represents an integer of 1 to 6, and preferably an integer of 1 to 4, more preferably an integer of 2 to 4.
通式(2)中的q表示0~3的整數,其中較佳為1~2的整數,更佳為1。 q in the formula (2) represents an integer of 0 to 3, and preferably an integer of 1 to 2, more preferably 1.
上述通式(2)所表示的化合物中,由所得到的樹脂組成物的安定性的觀點而言,較佳為q=1、R3為甲基、R4為氫原子之下述通式(2a)所表示的2級硫醇化合物。 In the compound represented by the above formula (2), from the viewpoint of the stability of the obtained resin composition, it is preferred that q = 1, R 3 is a methyl group, and R 4 is a hydrogen atom. The second-order thiol compound represented by (2a).
(上述通式(2a)中,p表示1~6的整數,A表示p價的有機基)。 (In the above formula (2a), p represents an integer of 1 to 6, and A represents a p-valent organic group).
通式(2)及(2a)中的A表示p價的有機基,具體而言為1~6價的有機基。 A in the general formulae (2) and (2a) represents a p-valent organic group, specifically, a 1 to 6-valent organic group.
作為1價的有機基,可舉例如碳數1~12之烷基、碳數3~12之環烷基、碳數6~24之芳基、碳數6~24之芳烷基、羰基(代表-CO-R,但R為烴基(較佳為碳數1~6之烷基))、酯基(代表-CO-O-R或-O-CO-R,但R為烴基(較佳為碳數1~6之烷基))、胺甲醯基等。 Examples of the monovalent organic group include an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aralkyl group having 6 to 24 carbon atoms, and a carbonyl group ( Represents -CO-R, but R is a hydrocarbyl group (preferably an alkyl group having 1 to 6 carbon atoms), an ester group (representing -CO-OR or -O-CO-R, but R is a hydrocarbyl group (preferably carbon) Alkyl groups of 1 to 6), an amine carbenyl group, and the like.
作為碳數1~12之烷基,可舉例如上述通式(1)中,舉例作為R2之基。 The alkyl group having 1 to 12 carbon atoms may, for example, be a group of R 2 in the above formula (1).
作為碳數3~12之環烷基,可舉例如環丙基、環丁基、環戊基、環己基、1-金剛烷基、2-金剛烷基、1-降莰基、2-降莰基等。 Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, a 1-norbornyl group, and a 2-norst.莰基等.
作為碳數6~24之芳基,可舉例如苯基、聯苯基、萘基等。 Examples of the aryl group having 6 to 24 carbon atoms include a phenyl group, a biphenyl group, and a naphthyl group.
作為碳數6~24之芳烷基,可舉例如苯甲基、苯乙基、苯丙基等。 Examples of the aralkyl group having 6 to 24 carbon atoms include a benzyl group, a phenethyl group, and a phenylpropyl group.
作為2價的有機基,可舉例如碳數1~12之伸烷基、碳數3~12之伸環烷基、伸苯基、伸聯苯基等之碳數6~24之伸芳基、聚醚基、聚矽氧烷基、羰基、酯基、醯胺基、胺酯基等。 The divalent organic group may, for example, be an alkylene group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, a biphenyl group or the like having 6 to 24 carbon atoms. , polyether group, polyoxyalkylene group, carbonyl group, ester group, decylamino group, amine ester group and the like.
作為碳數1~12之伸烷基,可舉例如亞甲基、伸乙基、伸正丙基、伸異丙基、伸正丁基、伸異丁基、伸戊基、 伸己基、伸庚基、伸辛基、2-伸乙基己基、伸壬基、伸癸基、伸十一基、伸十二基等。 Examples of the alkylene group having 1 to 12 carbon atoms include a methylene group, an ethylidene group, a propylidene group, an extended isopropyl group, an exobutyl group, an exobutyl group, and a pentyl group. Stretching hexyl, stretching heptyl, stretching octyl, 2-extended ethylhexyl, stretching thiol, stretching thiol, stretching eleven, extending twelve base.
作為碳數3~12之伸環烷基,可舉例如伸環丙基、伸環丁基、伸環戊基、伸環己基、伸環辛基、伸環癸基、1,3-伸金剛烷基等。 Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclobutene butyl group, a cyclopentylene group, a cyclohexylene group, a cyclooctyl group, a fluorenyl group, and a 1,3-extension ring. Alkyl and the like.
作為伸芳基,可舉例如1,2-伸苯基、1,3-伸苯基、1,4-伸苯基等之伸苯基、伸聯苯基、伸萘基等。 Examples of the extended aryl group include a stretching phenyl group such as a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group, a stretching phenyl group, an anthranyl group, and the like.
作為聚醚基,可舉例如聚環氧乙烷基、聚環氧丙烷基等。 The polyether group may, for example, be a polyethylene oxide group or a polypropylene oxide group.
作為聚矽氧烷基,可舉例如聚二甲基矽氧烷、聚二乙基矽氧烷、聚苯基矽氧烷、聚甲基苯基矽氧烷等。 The polyoxyalkylene group may, for example, be polydimethylsiloxane, polydimethoxysiloxane, polyphenylsiloxane or polymethylphenyloxane.
作為3~6價的有機基,可舉例如具有脂肪族鏈之3~6價的碳數1~12之脂肪族烴基、具有脂環結構之3~6價的碳數3~12之脂環式烴基、具有芳香環結構之3~6價的碳數6~24之芳香族烴基、及含有氧原子、氮原子、硫原子等之雜原子的具有雜環結構之3~6價的雜環基等。 Examples of the organic group having 3 to 6 valences include an aliphatic hydrocarbon group having a carbon number of 1 to 12 having a 3 to 6 valence of an aliphatic chain, and an alicyclic ring having a carbon number of 3 to 12 having an alicyclic structure of 3 to 6 carbon atoms. a hydrocarbon group, a 3 to 6-valent aromatic hydrocarbon group having an aromatic ring structure of 6 to 24, and a 3 to 6-valent heterocyclic ring having a heterocyclic structure containing a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom. Base.
此外,這些有機基A可進一步具有取代基。 Further, these organic groups A may further have a substituent.
有機基A可具有之取代基,可舉例如羥基、鹵素原子、烷基、環烷基、芳基、芳烷基、羰基、醛基、酯基、醯胺基、烷氧基、芳氧基、烷硫基、芳硫基、胺基、矽基、矽氧基等。 The organic group A may have a substituent, and examples thereof include a hydroxyl group, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a carbonyl group, an aldehyde group, an ester group, a decylamino group, an alkoxy group, and an aryloxy group. An alkylthio group, an arylthio group, an amine group, a decyl group, a decyloxy group or the like.
這些以A表示之p價有機基中,較佳為下述通式(C-1)或(C-2)所表示的基,或碳數1~12的伸烷基。 Among these p-valent organic groups represented by A, a group represented by the following formula (C-1) or (C-2) or an alkylene group having 1 to 12 carbon atoms is preferable.
上述(C-1)或(C-2)中,*表示鍵結部分,X1~X7各自獨立地表示單鍵、或可具有取代基之碳數1~12的伸烷基。作為該取代基,可舉例如與上述的有機基A可具有之取代基相同之物。 In the above (C-1) or (C-2), * represents a bonding moiety, and X 1 to X 7 each independently represent a single bond or an alkylene group having 1 to 12 carbon atoms which may have a substituent. The substituent may, for example, be the same as the substituent which the above-mentioned organic group A may have.
作為X1~X7,較佳為單鍵、或碳數1~8的伸烷基,更佳為碳數1~4的伸烷基,進一步較佳為亞甲基或伸乙基。 X 1 to X 7 is preferably a single bond or an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, further preferably a methylene group or an ethylidene group.
作為碳數1~12之伸烷基,較佳為碳數1~8之伸烷基,更佳為碳數1~6之伸烷基,進一步較佳為碳數2~4之伸烷基。 The alkylene group having 1 to 12 carbon atoms is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, further preferably an alkylene group having 2 to 4 carbon atoms. .
作為(C)成分之具體的化合物,可舉例如1,4-雙(3-巰基丁醯基氧基)丁烷、1,3,5-參(3-巰基丁醯基氧乙基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、季戊四醇肆(3-巰基丁酸酯)等。 Specific examples of the component (C) include 1,4-bis(3-mercaptobutyloxy)butane and 1,3,5-gin(3-mercaptobutyloxyethyl)-1,3. 5-triazine-2,4,6(1H,3H,5H)-trione, pentaerythritol bismuth (3-mercaptobutyrate), and the like.
這些化合物可單獨或組合兩種以上使用。 These compounds may be used alone or in combination of two or more.
此外,這些化合物,可從昭和電工(股)取得Karenz MT系列(「Karenz MT BD1」、「Karenz MT NR1」、「Karenz MT PE1」等)。 In addition, these compounds are available from Showa Denko Co., Ltd. in the Karenz MT series ("Karenz MT BD1", "Karenz MT NR1", "Karenz MT PE1", etc.).
本發明之樹脂組成物中(C)成分的含量,由所得到 的樹脂組成物在遮光部中的硬化性及耐溼熱信賴性的觀點而言,對於樹脂組成物中(A)~(C)成分的總量,較佳為1~30質量%,更佳為2~20質量%,進一步較佳為3~12質量%。 The content of the component (C) in the resin composition of the present invention is obtained from The resin composition is preferably from 1 to 30% by mass, more preferably from 1 to 30% by mass, based on the total amount of the components (A) to (C) in the resin composition, from the viewpoint of the curability and the resistance to moisture and heat resistance in the light-shielding portion. 2 to 20% by mass, further preferably 3 to 12% by mass.
<(D)成分:光聚合起始劑> <(D) component: photopolymerization initiator>
本發明所使用之光聚合起始劑(D),可舉例如二苯甲酮、N,N’-四甲基-4,4’-二胺基二苯甲酮(米其勒酮)、N,N-四乙基-4,4’-二胺基二苯甲酮、4-甲氧基-4’-二甲基胺基二苯甲酮、α-羥基異丁基苯酮、2-乙基蒽醌、第三丁基蒽醌、1,4-二甲基蒽醌、1-氯蒽醌、2,3-二氯蒽醌、3-氯-2-甲基蒽醌、1,2-苯并蒽醌、2-苯基蒽醌、1,4-萘醌、9,10-菲醌、硫代氧雜蒽酮、2-氯硫代氧雜蒽酮、1-羥基環己基苯酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、2-羥基-2-甲基-1-苯基丙烷-1-酮等之芳香族酮化合物;安息香、甲基安息香、乙基安息香等之安息香化合物;安息香甲醚、安息香乙醚、安息香異丁醚、安息香苯醚等之安息香醚化合物;1-羥基環己基苯酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、1-〔4-(2-羥基乙氧基)-苯基〕-2-羥基-2-甲基-1-丙烷-1-酮等之α-羥基烷基苯酮系化合物;雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基-戊基氧化膦、2,4,6-三甲基苯甲醯基-二苯基氧化膦等之醯基氧化膦系化合物;寡(2-羥基-2-甲基-1-(4-(1-甲基乙烯基)苯基)丙酮);β-(吖啶-9-基)丙烯酸的酯化合物;9 -苯基吖啶、9-吡啶基吖啶、1,7-二吖啶基庚烷等之吖啶化合物;2-(鄰氯苯基)-4,5-二苯基咪唑二聚物、2-(鄰氯苯基)-4,5-二(間甲氧基苯基)咪唑二聚物、2-(鄰氟苯基)-4,5-二苯基咪唑二聚物、2-(鄰甲氧基苯基)-4,5-二苯基咪唑二聚物、2-(對甲氧基苯基)-4,5-二苯基咪唑二聚物、2,4-二(對甲氧基苯基)-5-苯基咪唑二聚物、2-(2,4-二甲氧基苯基)-4,5-二苯基咪唑二聚物、2-(對甲基巰基苯基)-4,5-二苯基咪唑二聚物等之2,4,5-三芳基咪唑二聚物;二苯基乙二酮、2,2-二乙氧基苯乙酮、苯甲基二甲基縮酮、2-苯甲基-2-二甲基胺基-1-(4-嗎啉基苯基)-1-丁酮、2-甲基-1-〔4-(甲基硫基)苯基〕-2-嗎啉基-1-丙烷等。 The photopolymerization initiator (D) used in the present invention may, for example, be benzophenone or N,N'-tetramethyl-4,4'-diaminobenzophenone (michlerone). N,N-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, α-hydroxyisobutylbenzophenone, 2 -ethyl hydrazine, tert-butyl hydrazine, 1,4-dimethyl hydrazine, 1-chloroindole, 2,3-dichloropurine, 3-chloro-2-methylindole, 1 , 2-benzopyrene, 2-phenylindole, 1,4-naphthoquinone, 9,10-phenanthrenequinone, thioxanthone, 2-chlorothioxanthone, 1-hydroxyl ring Aromatic ketones such as hexyl benzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one a compound; a benzoin compound such as benzoin, methyl benzoin, ethyl benzoin; a benzoin ether compound such as benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin phenyl ether; 1-hydroxycyclohexyl benzophenone, 2-hydroxy-2 -methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, etc. Alpha-hydroxyalkylphenone compound; bis(2,4,6-trimethylbenzhydrazide) )-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzhydrazide Thiol-based phosphine oxide compound such as bis-diphenylphosphine oxide; oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)acetone); β-(吖Ester compound of pyridin-9-yl)acrylic acid; An acridine compound such as phenyl acridine, 9-pyridyl acridine or 1,7-diacridine heptane; 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di ( p-Methoxyphenyl)-5-phenylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methyl 2,4,5-triarylimidazole dimer such as nonylphenyl)-4,5-diphenylimidazole dimer; diphenylethylenedione, 2,2-diethoxyacetophenone, Benzyl dimethyl ketal, 2-benzyl-2- dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 2-methyl-1-[4- (Methylthio)phenyl]-2-morpholinyl-1-propane and the like.
這些光聚合起始劑(D)可單獨或組合兩種以上使用。 These photopolymerization initiators (D) may be used singly or in combination of two or more.
這些之中,由抑制樹脂組成物變色的觀點而言,較佳為1-羥基環己基苯酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、1-〔4-(2-羥基乙氧基)-苯基〕-2-羥基-2-甲基-1-丙烷-1-酮等之α-羥基烷基苯酮系化合物、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基-戊基氧化膦、2,4,6-三甲基苯甲醯基-二苯基氧化膦等之醯基氧化膦系化合物、寡(2-羥基-2-甲基-1-(4-(1-甲基乙烯基)苯基)丙酮),及這些的組合。 Among these, from the viewpoint of suppressing discoloration of the resin composition, 1-hydroxycyclohexyl benzophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 1-[4 are preferable. An α-hydroxyalkylphenone compound such as -(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, bis(2,4,6- Trimethyl benzhydryl)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, 2,4,6 a mercapto phosphine oxide compound such as trimethylbenzhydryl-diphenylphosphine oxide or oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl) Acetone), and combinations of these.
又,由得到適合製作厚膜之薄片之樹脂組成物的觀點而言,較佳為雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、 雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基-戊基氧化膦、2,4,6-三甲基苯甲醯基-二苯基氧化膦等之醯基氧化膦系化合物。 Further, from the viewpoint of obtaining a resin composition suitable for producing a thin film sheet, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide is preferred. Bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzylidene-diphenylphosphine oxide A sulfhydryl phosphine-based compound.
本發明所使用之(D)光聚合起始劑的含量,由硬化性的觀點而言,相對於(A)~(C)成分的總量100質量份,較佳為0.05~10質量份,更佳為0.08~7質量份,進一步較佳為0.1~4質量份,更佳為0.2~2質量份。 The content of the (D) photopolymerization initiator used in the present invention is preferably 0.05 to 10 parts by mass, based on 100 parts by mass of the total of the components (A) to (C), from the viewpoint of curability. More preferably, it is 0.08 to 7 parts by mass, further preferably 0.1 to 4 parts by mass, more preferably 0.2 to 2 parts by mass.
<其他添加劑> <Other additives>
本發明之光硬化性樹脂組成物,在不妨礙本發明的效果之範圍內,可進一步調配其他添加劑。作為其他添加劑,可舉例如安定劑、塑化劑等。 The photocurable resin composition of the present invention can be further formulated with other additives within a range that does not impair the effects of the present invention. As another additive, a stabilizer, a plasticizer, etc. are mentioned, for example.
安定劑是以提升光硬化性樹脂組成物的安定性為目的來添加,可舉例如亞磷酸三苯酯等。 The stabilizer is added for the purpose of improving the stability of the photocurable resin composition, and examples thereof include triphenyl phosphite.
塑化劑是以調整光硬化性樹脂組成物的黏度為目的來添加,可舉例如二質子酸雨多價醇之聚酯系塑化劑;分子鏈為丙烯酸烷基酯單體單元及/或甲基丙烯酸烷基酯單體單元所成之液狀丙烯酸樹脂系塑化劑;聚丙二醇或其衍生物等之聚醚系系塑化劑;胺酯系塑化劑;聚-α-甲基苯乙烯、聚苯乙烯等之聚苯乙烯系塑化劑等。 The plasticizer is added for the purpose of adjusting the viscosity of the photocurable resin composition, and examples thereof include a polyester-based plasticizer of a diproton acid rain polyvalent alcohol; and the molecular chain is an alkyl acrylate monomer unit and/or a Liquid acrylic resin-based plasticizer composed of alkyl acrylate monomer unit; polyether-based plasticizer such as polypropylene glycol or its derivative; amine ester plasticizer; poly-α-methylbenzene A polystyrene plasticizer such as ethylene or polystyrene.
又,本發明之光硬化性樹脂組成物,由耐溼熱信賴性及抑制硬化物中產生氣泡的觀點而言,較佳為實質上不含有機溶劑。 Moreover, it is preferable that the photocurable resin composition of the present invention contains substantially no organic solvent from the viewpoint of moisture and heat resistance and suppression of generation of bubbles in the cured product.
此外,「實質上不含有機溶劑」,意謂不刻意添加有機溶劑,在不使本發明之光硬化性樹脂組成物的光硬化後特性降 低的程度時,可含有微量的有機溶劑。 Further, "substantially free of an organic solvent" means that an organic solvent is not intentionally added, and the characteristics are lowered without photohardening the photocurable resin composition of the present invention. At a low level, a trace amount of an organic solvent may be contained.
具體而言,有機溶劑的含量,相對於樹脂組成物的總量,在1000ppm以下即可,較佳為500ppm以下,更佳為100ppm以下,進一步較佳為10ppm以下,最佳為完全不含有機溶劑(0ppm)。 Specifically, the content of the organic solvent may be 1000 ppm or less, preferably 500 ppm or less, more preferably 100 ppm or less, still more preferably 10 ppm or less, and most preferably no organic matter, based on the total amount of the resin composition. Solvent (0 ppm).
在此,「有機溶劑」意指分子內不具有乙烯性不飽和基,在25℃時為液狀,且一大氣壓時的沸點在250℃以下之有機化合物。 Here, the "organic solvent" means an organic compound which does not have an ethylenically unsaturated group in the molecule, is liquid at 25 ° C, and has a boiling point of 250 ° C or less at an atmospheric pressure.
本發明之光硬化性樹脂組成物在25℃時的黏度,由抑制滲漏及操作性的觀點而言,較佳為500~5000mPa.s,更佳為1,000~5,000mPa˙s,進一步較佳為2,000~4,000mPa.s,更佳為2,500~3,800mPa.s。 The viscosity of the photocurable resin composition of the present invention at 25 ° C is preferably from 500 to 5,000 mPa from the viewpoint of suppressing leakage and handling properties. s, more preferably 1,000 to 5,000 mPa ̇ s, further preferably 2,000 to 4,000 mPa. s, more preferably 2,500~3,800mPa. s.
此外,25℃時的黏度是使用E型黏度計,利用3° cone rotor、0.5min-1測定之值,具體而言是基於實施例所記載的測定方法所得之值。 Further, the viscosity at 25 ° C is a value measured by a 3° cone rotor and 0.5 min −1 using an E-type viscometer, specifically, a value obtained by the measurement method described in the examples.
本發明之光硬化性樹脂組成物的硬化物,在膜厚175nm時的波長440nm之透光率,較佳為98%以上,更佳為99%以上。 The cured product of the photocurable resin composition of the present invention preferably has a light transmittance at a wavelength of 440 nm at a film thickness of 175 nm of 98% or more, more preferably 99% or more.
本發明之光硬化性樹脂組成物的硬化物的折射率,較佳為1.45~1.55,更佳為1.47~1.53。 The refractive index of the cured product of the photocurable resin composition of the present invention is preferably from 1.45 to 1.55, more preferably from 1.47 to 1.53.
本發明之光硬化性樹脂組成物的硬化物在頻率1MHz時之介電常數,較佳為2.5~3.0,更佳為2.7~2.9。該 介電常數若在2.5以上,則將本發明之樹脂組成物應用於觸控面板用途之情況,可提高觸控面板的感應性能。另一方面,該介電常數若在3.0以下,則應用於觸控面板用途之情況,可抑制感應過大而產生故障。 The dielectric constant of the cured product of the photocurable resin composition of the present invention at a frequency of 1 MHz is preferably from 2.5 to 3.0, more preferably from 2.7 to 2.9. The When the dielectric constant is 2.5 or more, when the resin composition of the present invention is applied to a touch panel application, the sensing performance of the touch panel can be improved. On the other hand, when the dielectric constant is 3.0 or less, it is applied to a touch panel application, and it is possible to suppress an excessive inductance and cause a malfunction.
此外,這些物性值是基於實施例所記載的測定方法所得之值。 Further, these physical property values are values obtained based on the measurement methods described in the examples.
本發明之影像顯示用裝置,是具有積層結構之影像顯示用裝置,該積層結構包含:影像顯示元件,其具有影像顯示部;保護面板,其具有沿著外周邊的遮光部;及,樹脂層,其存在於前述影像顯示元件與前述保護面板之間;其中,前述樹脂層是上述液狀光硬化性樹脂組成物的硬化物。 The image display device of the present invention is an image display device having a laminated structure, the laminated structure comprising: an image display element having an image display portion; a protective panel having a light shielding portion along the outer periphery; and a resin layer The resin layer is present between the image display element and the protective panel; wherein the resin layer is a cured product of the liquid photocurable resin composition.
又,本發明之影像顯示用裝置,是具有積層結構之影像顯示用裝置,該積層結構包含:影像顯示元件,其具有影像顯示部;觸控面板;保護面板,其具有沿著外周邊的遮光部;及,樹脂層,其存在於前述觸控面板與前述保護面板之間;其中,前述樹脂層是上述液狀光硬化性樹脂組成物的硬化物。 Moreover, the image display device of the present invention is a video display device having a laminated structure, the laminated structure including: an image display device having an image display portion; a touch panel; and a protective panel having a light shielding along the outer periphery And a resin layer existing between the touch panel and the protective panel; wherein the resin layer is a cured product of the liquid photocurable resin composition.
繼而,說明影像顯示用裝置的一例也就是液晶顯示裝置。 Next, an example of the image display device will be described as a liquid crystal display device.
以下說明藉由使用本實施形態之光硬化性樹脂組成物,可製造的影像顯示用裝置的一例也就是液晶顯示裝置。 In the following, an example of a video display device which can be manufactured by using the photocurable resin composition of the present embodiment is a liquid crystal display device.
<液晶顯示用裝置> <LCD display device>
第1圖是示意性地表示本發明之影像顯示用裝置的一例也就是液晶顯示裝置的一實施形態的側面剖面圖。 Fig. 1 is a side cross-sectional view schematically showing an embodiment of a liquid crystal display device which is an example of the image display device of the present invention.
第1圖所表示的液晶顯示用裝置1A,由影像顯示元件1、 樹脂層32、及保護面板40所構成,其中,影像顯示元件1是由背光系統50、偏光板22、液晶顯示單元10及偏光板20依照此順序積層而成;樹脂層32設置在作為液晶顯示用裝置的視認側之偏光板20的上面;保護面板40設置於樹脂層32的表面。樹脂層32是由本實施形態的光硬化性樹脂組成物的硬化物所構成。又,保護面板40具有沿著該保護面板的外周邊的遮光部41。 The liquid crystal display device 1A shown in Fig. 1 is composed of the image display element 1. The resin layer 32 is formed by the backlight system 50, the polarizing plate 22, the liquid crystal display unit 10, and the polarizing plate 20 in this order; the resin layer 32 is provided as a liquid crystal display. The upper surface of the polarizing plate 20 on the viewing side of the device is used; and the protective panel 40 is provided on the surface of the resin layer 32. The resin layer 32 is composed of a cured product of the photocurable resin composition of the present embodiment. Further, the protective panel 40 has a light blocking portion 41 along the outer periphery of the protective panel.
又,第2圖是示意性地表示本發明之影像顯示用裝置的一例也就是液晶顯示裝置的一實施形態,亦即示意性地表示配備有觸控面板之液晶顯示裝置的側面剖面圖。第2圖所表示的液晶顯示用裝置1B,由影像顯示元件1、樹脂層32、觸控面板30、樹脂層31、及保護面板40所構成,其中,影像顯示元件1是由背光系統50、偏光板22、液晶顯示單元10及偏光板20依照此順序積層而成;樹脂層32設置在作為液晶顯示用裝置的視認側之偏光板20的上面;觸控面板30設置在樹脂層32的上面;樹脂層31設置在觸控面板30的上面;保護面板40設置於樹脂層31的表面。又,保護面板40具有沿著該保護面板的外周邊的遮光部41。 In addition, FIG. 2 is a side cross-sectional view schematically showing an embodiment of a liquid crystal display device, which is an example of a liquid crystal display device, which is an example of a liquid crystal display device. The liquid crystal display device 1B shown in FIG. 2 is composed of a video display element 1, a resin layer 32, a touch panel 30, a resin layer 31, and a protective panel 40, wherein the image display element 1 is composed of a backlight system 50, The polarizing plate 22, the liquid crystal display unit 10, and the polarizing plate 20 are laminated in this order; the resin layer 32 is provided on the upper surface of the polarizing plate 20 as the viewing side of the liquid crystal display device; and the touch panel 30 is disposed on the resin layer 32. The resin layer 31 is disposed on the upper surface of the touch panel 30; and the protective panel 40 is disposed on the surface of the resin layer 31. Further, the protective panel 40 has a light blocking portion 41 along the outer periphery of the protective panel.
此外,第2圖的液晶顯示用裝置中,樹脂層介於影像顯示元件1與觸控面板30之間、及觸控面板30與保護面板40之間的雙方,但樹脂層介於上述其中一方面即可。又,觸控板為on-cell型式之情況,則觸控板與液晶顯示單元整合為一體。作為具體例,可舉例如第1圖之液晶顯示用裝置的液晶顯示單元10,其被取代為on-cell型式。 Further, in the liquid crystal display device of FIG. 2, the resin layer is interposed between the image display element 1 and the touch panel 30, and between the touch panel 30 and the protective panel 40, but the resin layer is interposed therebetween. Aspects can be. Moreover, when the touch panel is of the on-cell type, the touch panel is integrated with the liquid crystal display unit. As a specific example, for example, the liquid crystal display unit 10 of the liquid crystal display device of Fig. 1 is replaced with an on-cell type.
根據第1圖及第2圖所表示的液晶顯示用裝置,其具備本發明之光硬化性樹脂組成物的硬化物作為樹脂層31或32,故具有耐撞擊性,可得到無畫面殘影而鮮明且高對比的影像。 According to the liquid crystal display device shown in FIG. 1 and FIG. 2, since the cured product of the photocurable resin composition of the present invention is provided as the resin layer 31 or 32, it has impact resistance and can be obtained without image sticking. Bright and highly contrasting images.
液晶顯示單元10,可使用該技術領域內習知之液晶材料所構成之產品。又,液晶材料的控制方式可分為:TN(Twisted Nematic)方式、STN(Super-Twisted Nematic)方式、VA(Vertical Alignment)方式、IPS(In-Place-Switching)方式等,但在本發明,液晶顯示單元使用何種控制方法均可。 The liquid crystal display unit 10 can be made of a liquid crystal material known in the art. Further, the control method of the liquid crystal material can be classified into a TN (Twisted Nematic) method, an STN (Super-Twisted Nematic) method, a VA (Vertical Alignment) method, an IPS (In-Place-Switching) method, etc., but in the present invention, What control method can be used for the liquid crystal display unit.
作為偏光板20及22,可使用該技術領域內一般的偏光板。這些偏光板的表面亦可進行防反射、防污、表面硬化處理(hard coat)等處理。這些表面處理施行於偏光板的單面或雙面皆可。 As the polarizing plates 20 and 22, a polarizing plate generally used in the art can be used. The surfaces of these polarizers can also be treated with anti-reflection, anti-fouling, hard coat, and the like. These surface treatments can be applied to one or both sides of the polarizing plate.
作為觸控板30,可使用該技術領域內一般使用之觸控板。 As the touch panel 30, a touch panel generally used in the art can be used.
樹脂層31及32,可形成舉例如0.02mm~3mm之厚度。尤其本發明之液狀硬化性樹脂組成物,可有效地形成厚膜,適合形成0.1mm以上之樹脂層31及32。 The resin layers 31 and 32 may be formed to have a thickness of, for example, 0.02 mm to 3 mm. In particular, the liquid curable resin composition of the present invention can form a thick film efficiently, and is suitable for forming resin layers 31 and 32 of 0.1 mm or more.
作為保護面板40,可使用一般的光學用透明基材。 As the protective panel 40, a general transparent substrate for optics can be used.
作為該光學用透明基材,可舉例如玻璃板、石英板等無機物基板;壓克力板、聚碳酸酯等之樹脂基板;厚聚酯薄片等樹脂薄片。需要高表面硬度之情況,較佳為玻璃板、壓克力板等,更佳為玻璃板。 Examples of the transparent substrate for optics include inorganic substrates such as glass plates and quartz plates; resin substrates such as acrylic sheets and polycarbonate; and resin sheets such as thick polyester sheets. In the case where a high surface hardness is required, a glass plate, an acrylic plate or the like is preferable, and a glass plate is more preferable.
又,這些光學用透明基板的表面亦可進行防反射、防污、表面硬化處理等處理。這些表面處理施行於該基板的單面或 雙面皆可。又,該基板可由多枚基板組合使用。 Moreover, the surface of these optical transparent substrates can also be subjected to treatment such as antireflection, antifouling, and surface hardening treatment. These surface treatments are applied to one side of the substrate or Both sides are available. Further, the substrate can be used in combination of a plurality of substrates.
又,以提高顯示影像的對比為目的,由這些基板所成之保護面板40,設有以規定寬度之框狀沿著該保護面板的外周邊的遮光部41。該遮光部41,具有遮蔽影像顯示用面板周邊部之不必要光、防止漏光導致顯示品質降低的功能。 Further, for the purpose of improving the contrast of the display image, the protective panel 40 made of these substrates is provided with a light blocking portion 41 having a frame shape having a predetermined width along the outer periphery of the protective panel. The light shielding portion 41 has a function of shielding unnecessary light in the peripheral portion of the image display panel and preventing light leakage from deteriorating in display quality.
背光系統50的結構並無特別限制,一般而言有反射板等反射手段及燈泡等照明手段。這些反射手段與照明手段可使用一般影像顯示用裝置內習知的手段。 The configuration of the backlight system 50 is not particularly limited, and generally includes a reflecting means such as a reflecting plate and an illumination means such as a bulb. These means of reflection and illumination means can be used by conventional means in a general image display device.
本發明之影像顯示用裝置的製造方法,是先將具有影像顯示部之影像顯示元件或觸控面板,與具有沿著外周邊的遮光部之保護面板對向配置,然後使液狀光硬化性樹脂組成物介於這些構件的間隙中,並使該光硬化性樹脂組成物硬化,來製造影像顯示用裝置的方法,其中,使本發明之液狀光硬化性樹脂組成物介於前述間隙中,並至少自前述保護面板側進行光照射來使其硬化。 In the method of manufacturing the image display device of the present invention, the image display element or the touch panel having the image display unit is disposed opposite to the protective panel having the light shielding portion along the outer periphery, and then the liquid photocurability is performed. A method of producing a device for image display in which a resin composition is interposed between the gaps of the members and curing the photocurable resin composition, wherein the liquid photocurable resin composition of the present invention is interposed in the gap And at least light-irradiated from the side of the protective panel to harden it.
例如,第1圖的液晶顯示用裝置1A,是先將影像顯示元件1與具有沿著外周邊的遮光部41之保護面板40對向配置,然後使本發明之液狀光硬化性樹脂組成物介於這些構件的間隙中,並至少自該保護面板側進行光照射來使上述光硬化性樹脂組成物硬化,而形成樹脂層32來製造。 For example, in the liquid crystal display device 1A of Fig. 1, the image display element 1 is placed opposite to the protective panel 40 having the light shielding portion 41 along the outer periphery, and then the liquid photocurable resin composition of the present invention is placed. The resin layer 32 is formed by curing the photocurable resin composition at least from the protective panel side by light irradiation at least on the protective panel side.
又,第2圖的配備有觸控面板之液晶顯示用裝置1B,是先將影像顯示元件1、觸控面板30、以及具有沿著外周邊的遮光部41之保護面板40對向配置,然後使本發明之 液狀光硬化性樹脂組成物介於至少觸控面板30與保護面板的間隙中,並至少自該保護面板側進行光照射來使上述光硬化性樹脂組成物硬化,而形成樹脂層31來製造。此外,亦可使本發明之液狀光硬化性樹脂組成物介於影像顯示元件1與觸控板30的間隙中,同樣地使該樹脂組成物硬化,而形成樹脂層32。 Moreover, in the liquid crystal display device 1B equipped with the touch panel of FIG. 2, the image display element 1, the touch panel 30, and the protective panel 40 having the light shielding portion 41 along the outer periphery are disposed oppositely, and then Making the invention The liquid photocurable resin composition is interposed between at least the gap between the touch panel 30 and the protective panel, and is light-irradiated from at least the protective panel side to cure the photocurable resin composition to form the resin layer 31. . Further, the liquid photocurable resin composition of the present invention may be interposed between the image display element 1 and the touch panel 30, and the resin composition may be cured in the same manner to form the resin layer 32.
在此,例如使用以往的光硬化性樹脂組成物來製造液晶顯示用裝置的情況,在相當於第1圖及第2圖的P部分之遮光部41的背側部分的空間內,對於所填充之光硬化性樹脂組成物,無法到達充分的光線,而妨礙硬化,造成遮光部周邊的光硬化性樹脂組成物的硬化無法充分進行,而大幅損害影像顯示用裝置的品質並招致信賴性降低。 Here, for example, when a liquid crystal display device is manufactured using a conventional photocurable resin composition, the space is filled in a space corresponding to the back side portion of the light shielding portion 41 of the P portion of the first and second figures. The photocurable resin composition does not reach sufficient light, and hinders hardening, and the curing of the photocurable resin composition around the light-shielding portion is not sufficiently performed, and the quality of the image display device is greatly impaired, and the reliability is lowered.
然而,在本發明之影像顯示用裝置的製造方法中,因使用具有優異硬化性的本發明之光硬化性樹脂組成物,故照射紫外線時,不只是相當於第1圖及第2圖的Q部分之透光部,該透光部(Q部分)附近的紫外線不直接照射之遮光部41的背側部分(P部分)亦可硬化。因此,根據本發明之影像顯示用裝置的製造方法,可由良好生產性來製造品質優良的影像顯示用裝置。 However, in the method for producing an image display device of the present invention, since the photocurable resin composition of the present invention having excellent curability is used, it is not only the Q corresponding to the first and second figures when irradiated with ultraviolet rays. In the partial light transmitting portion, the back side portion (P portion) of the light shielding portion 41 where the ultraviolet rays in the vicinity of the light transmitting portion (Q portion) are not directly irradiated may be hardened. Therefore, according to the method for manufacturing an image display device of the present invention, an image display device of excellent quality can be manufactured with good productivity.
此外,作為使光硬化性樹脂組成物介於上述構件的間隙之方法,可舉例如使用分配器,將該樹脂組成物塗佈於影像顯示單元、觸控面板或保護面板上之後,以真空(減壓)或大氣壓使之貼合;或在隔開一定間隔而配製的空間部分內,將光硬化性樹脂組成物注模於其中等方法。此外,將光 硬化性樹脂組成物注模時,可在影像顯示單元及保護面板周圍製作一擋閘(dam)。 Further, as a method of allowing the photocurable resin composition to be interposed between the gaps of the members, for example, a dispenser is used, and after applying the resin composition to an image display unit, a touch panel or a protective panel, vacuum is applied ( The method is carried out by applying a photocurable resin composition to a space portion which is prepared at a predetermined interval. In addition, the light will When the curable resin composition is molded, a dam can be formed around the image display unit and the protective panel.
光照射,可例如使用紫外線照射裝置,使其幾乎垂直於所填充之光硬化性樹脂組成物,由保護面板側照射紫外線。 The light irradiation can be performed, for example, by using an ultraviolet irradiation device so as to be almost perpendicular to the filled photocurable resin composition, and the ultraviolet rays are irradiated from the side of the protective panel.
此時的曝光量,較佳為500mJ/cm2~5000mJ/cm2。此外。曝光量是使用紫外線照度計(製品名「UV-M02」(受光器UV-36),ORC公司製)等可測定之照度乘上照射時間(秒)所得之值。 The exposure amount at this time is preferably 500 mJ/cm 2 to 5000 mJ/cm 2 . Also. The exposure amount is a value obtained by multiplying the illuminance which can be measured by the ultraviolet illuminometer (product name "UV-M02" (light receiver UV-36), ORC) by the irradiation time (second).
作為紫外線照射的光源,可舉例如低壓水銀燈、中壓水銀燈、高壓水銀燈、金屬鹵化物燈、LED燈泡等。這些之中,較佳為高壓水銀燈、金屬鹵化物燈。 Examples of the light source for ultraviolet irradiation include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an LED bulb. Among these, a high pressure mercury lamp or a metal halide lamp is preferred.
此外,光照射時,可同時由保護面板側照射及由側面照射。又,光照射的同時可將含有光硬化性樹脂組成物之積層體加熱等,來促進硬化。 In addition, when the light is irradiated, it can be simultaneously irradiated from the side of the protective panel and irradiated from the side. In addition, the laminate containing the photocurable resin composition can be heated or the like to promote curing.
如上述說明,說明了可藉由使用本發明的光硬化性樹脂組成物來製造的影像顯示用裝置中的一種,也就是液晶顯示用裝置的技術,但可使用本發明的光硬化性樹脂組成物來製造的影像顯示用裝置,並未限定於液晶顯示用裝置。例如,亦可適用於電漿顯示器(PDP)、陰極射線管(CRT)、場發射顯示器(FED)、有機EL顯示器、3D顯示器、電子紙等。 As described above, one of the image display devices which can be produced by using the photocurable resin composition of the present invention, that is, the liquid crystal display device, has been described, but the photocurable resin of the present invention can be used. The image display device manufactured by the object is not limited to the liquid crystal display device. For example, it can also be applied to a plasma display (PDP), a cathode ray tube (CRT), a field emission display (FED), an organic EL display, a 3D display, an electronic paper, or the like.
以下,藉由實施例更詳細地說明本發明,但本發明 並未限定於下述實施例。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention It is not limited to the following examples.
首先,以下說明應用了本發明的影像顯示用裝置中,可使用之光硬化性樹脂組成物的合成例。 First, a synthesis example of a photocurable resin composition which can be used in the image display device to which the present invention is applied will be described below.
此外,下述合成例中,重量平均分子量(Mw)及數量平均分子量(Mn)是基於以下方法測定之值。 Further, in the following synthesis examples, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by the following methods.
使用膠體滲透層析儀(GPC)進行測定,以四氫呋喃(THF)作為溶劑,聚苯乙烯作為標準物。以下表示GPC的條件。 The measurement was carried out using a colloidal permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent and polystyrene as a standard. The conditions for GPC are shown below.
測定儀器:HLC-8320GPC(製品名,Tosoh(股)製) Measuring instrument: HLC-8320GPC (product name, manufactured by Tosoh Co., Ltd.)
分析管柱:TSKgel SuperMultipore HZ-H(3支連接)(製品名,Tosoh(股)製) Analysis column: TSKgel SuperMultipore HZ-H (3 connections) (product name, manufactured by Tosoh)
保護管柱:TSKguardcolumn SuperMP(HZ)-H(製品名,Tosoh(股)製) Protection column: TSKguardcolumn SuperMP (HZ)-H (product name, manufactured by Tosoh)
沖提液:THF Effervescent solution: THF
測定溫度:25℃ Measuring temperature: 25 ° C
(聚丁二烯甲基丙烯酸酯的合成) (Synthesis of polybutadiene methacrylate)
在具備冷卻管、溫度計、攪拌裝置、滴液漏斗及空氣注入管的反應容器內,加入α,ω-聚丁二烯二醇(日本曹達(股)製,商品名「聚丁二烯二醇G-3000」,〔1,2-結構單元/1,4-結構單元)的含量比例:90/10,羥值=27mgKOH/g)978.2質量份、對甲氧基酚0.5質量份作為聚合抑制劑、二月桂酸二丁基錫(東京Fine Chemical(股)製,商品名「L101」)0.05質量份作為觸媒。之後,反應器內一邊通入空氣一邊升 溫至70℃後,在70~75℃時一邊攪拌一邊滴入2-甲基丙烯酸異氰酸基乙酯(昭和電工(股)製,商品名「Karenz MOI」)20.3質量份,在1小時內平均滴入來進行反應。 In a reaction vessel equipped with a cooling tube, a thermometer, a stirring device, a dropping funnel, and an air injection tube, α,ω-polybutadiene diol (manufactured by Nippon Soda Co., Ltd., trade name "polybutadiene diol" is added. G-3000", [1, 2-structural unit / 1,4-structural unit) content ratio: 90/10, hydroxyl value = 27 mg KOH / g) 978.2 parts by mass, p-methoxyphenol 0.5 parts by mass as polymerization inhibition 0.05 parts by mass of dibutyltin dilaurate (manufactured by Tokyo Fine Chemical Co., Ltd., trade name "L101") was used as a catalyst. After that, the inside of the reactor is ventilated while passing air. After warming to 70 ° C, 20.3 parts by mass of 2-isopropy methacrylate (manufactured by Showa Denko Co., Ltd., product name "Karenz MOI") was added dropwise at 70 to 75 ° C for 1 hour. The average was dropped in to carry out the reaction.
滴入結束後,使其反應5小時,之後用IR測定之結果,確認異氰酸酯消失則終止反應,得到末端具有甲基丙烯醯基之聚丁二烯甲基丙烯酸酯(重量平均分子量7,700)。該聚丁二烯甲基丙烯酸酯一分子的甲基丙烯醯基之平均值(平均官能基數量)為0.5(由投入量計算之值)。 After the completion of the dropwise addition, the reaction was allowed to proceed for 5 hours. Then, the result of IR measurement confirmed that the isocyanate disappeared, and the reaction was terminated to obtain a polybutadiene methacrylate having a methacrylinyl group at the terminal (weight average molecular weight: 7,700). The average value (the average number of functional groups) of the methacryl fluorenyl group of one molecule of the polybutadiene methacrylate was 0.5 (the value calculated from the amount of input).
(氫化聚丁二烯甲基丙烯酸酯的合成) (Synthesis of hydrogenated polybutadiene methacrylate)
在具備冷卻管、溫度計、攪拌裝置、滴液漏斗及空氣注入管的反應容器內,加入氫化聚丁二烯二醇(日本曹達(股)製,商品名「聚丁二烯二醇GI-3000」,羥值=29mgKOH/g)1045.7質量份、對甲氧基酚0.5質量份作為聚合抑制劑、二月桂酸二丁基錫(東京Fine Chemical(股)製,商品名「L101」)0.05質量份作為觸媒。之後,反應器內一邊通入空氣一邊升溫至70℃後,在70~75℃時一邊攪拌一邊滴入2-甲基丙烯酸異氰酸基乙酯(昭和電工(股)製,商品名「Karenz MOI」)20.3質量份,在1小時內平均滴入來進行反應。 Hydrogenated polybutadiene diol (manufactured by Nippon Soda Co., Ltd., trade name "polybutadiene diol GI-3000" in a reaction vessel equipped with a cooling tube, a thermometer, a stirring device, a dropping funnel, and an air injection tube "Hydroxyl=29 mgKOH/g) 1045.7 parts by mass and p-methoxyphenol 0.5 parts by mass as a polymerization inhibitor and dibutyltin dilaurate (manufactured by Tokyo Fine Chemical Co., Ltd., trade name "L101") as 0.05 parts by mass. catalyst. After that, the temperature was raised to 70 ° C while the air was introduced into the reactor, and then 2-methyl methacrylate was added dropwise at 70 to 75 ° C (product of Showa Denko Co., Ltd.) under the trade name "Karenz". MOI") 20.3 parts by mass, which was dropped by an average of 1 hour to carry out a reaction.
滴入結束後,使其反應5小時,之後用IR測定之結果,確認異氰酸酯消失則終止反應,得到末端具有甲基丙烯醯基之氫化聚丁二烯甲基丙烯酸酯(重量平均分子量7,700)。該氫化聚丁二烯甲基丙烯酸酯一分子的甲基丙烯醯基之平均值 (平均官能基數量)為0.5(由投入量計算之值)。 After the completion of the dropwise addition, the reaction was allowed to proceed for 5 hours. Then, the result of IR measurement confirmed that the isocyanate disappeared, and the reaction was terminated to obtain a hydrogenated polybutadiene methacrylate having a methacryl oxime group at the terminal (weight average molecular weight: 7,700). The average value of one molecule of the hydrogenated polybutadiene methacrylate (the average number of functional groups) is 0.5 (the value calculated from the input amount).
(氫化異戊二烯甲基丙烯酸酯的合成) (Synthesis of hydrogenated isoprene methacrylate)
在具備冷卻管、溫度計、攪拌裝置、滴液漏斗及空氣注入管的反應容器內,加入末端羥基氫化異戊二烯(出光興產(股)製,商品名「Epole」,羥值=51mgKOH/g)843.3份、對甲氧基酚0.5質量份作為聚合抑制劑、二月桂酸二丁基錫(東京Fine Chemical(股)製,商品名「L101」)0.05質量份作為觸媒。之後,反應器內一邊通入空氣一邊升溫至70℃後,在70~75℃時一邊攪拌一邊滴入2-甲基丙烯酸異氰酸基乙酯(昭和電工(股)製,商品名「Karenz MOI」)20.3質量份,在1小時內平均滴入來進行反應。 In a reaction vessel equipped with a cooling tube, a thermometer, a stirring device, a dropping funnel, and an air injection tube, a terminal hydrogenated hydrogen isoprene (manufactured by Idemitsu Kosan Co., Ltd., trade name "Epole", hydroxyl value = 51 mgKOH / g) 843.3 parts, 0.5 parts by mass of p-methoxyphenol as a polymerization inhibitor, and 0.05 parts by mass of dibutyltin dilaurate (manufactured by Tokyo Fine Chemical Co., Ltd., trade name "L101") as a catalyst. After that, the temperature was raised to 70 ° C while the air was introduced into the reactor, and then 2-methyl methacrylate was added dropwise at 70 to 75 ° C (product of Showa Denko Co., Ltd.) under the trade name "Karenz". MOI") 20.3 parts by mass, which was dropped by an average of 1 hour to carry out a reaction.
滴入結束後,使其反應5小時,之後用IR測定之結果,確認異氰酸酯消失則終止反應,得到末端具有甲基丙烯醯基之氫化異戊二烯甲基丙烯酸酯(重量平均分子量7,700)。該氫化異戊二烯甲基丙烯酸酯一分子的甲基丙烯醯基之平均值(平均官能基數量)為0.5(由投入量計算之值)。 After the completion of the dropwise addition, the reaction was allowed to proceed for 5 hours. Then, the result of IR measurement confirmed that the isocyanate disappeared, and the reaction was terminated to obtain a hydrogenated isoprene methacrylate having a methyl methacrylate group at the terminal (weight average molecular weight: 7,700). The average value (the average number of functional groups) of the methacryl fluorenyl group of one molecule of the hydrogenated isoprene methacrylate was 0.5 (the value calculated from the input amount).
(丙二醇丙烯酸酯[PPGUA]的合成) (Synthesis of propylene glycol acrylate [PPGUA])
在具備冷卻管、溫度計、攪拌裝置、滴液漏斗及空氣注入管的反應容器內,加入聚丙二醇(分子量2,000)155質量份、2-羥基乙基丙烯酸酯17.9質量份、對甲氧基酚0.5質量份作為聚合抑制劑、二月桂酸二丁基錫0.05質量份作為觸媒。之後,反應器內一邊通入空氣一邊升溫至70℃後,在70 ~75℃時一邊攪拌一邊滴入2,2,4-三甲基六亞甲基二異氰酸酯32.4質量份,在2小時內平均滴入來進行反應。 In a reaction vessel equipped with a cooling tube, a thermometer, a stirring device, a dropping funnel, and an air injection tube, 155 parts by mass of polypropylene glycol (molecular weight: 2,000), 17.9 parts by mass of 2-hydroxyethyl acrylate, and p-methoxyphenol 0.5 were added. The mass part was used as a polymerization inhibitor and 0.05 parts by mass of dibutyltin dilaurate as a catalyst. After that, the temperature inside the reactor was increased to 70 ° C while passing air, and 70 At a temperature of ~75 ° C, 32.4 parts by mass of 2,2,4-trimethylhexamethylene diisocyanate was added dropwise thereto, and the mixture was dropped on the average over 2 hours to carry out a reaction.
滴入結束後,使其反應5小時,之後用IR測定之結果,確認異氰酸酯消失則終止反應,得到丙二醇丙烯酸酯[PPGUA],其將聚丙二醇與三甲基六亞甲基二異氰酸酯作為重複單元,且兩末端具有乙烯性不飽和鍵。該丙二醇丙烯酸酯一分子的乙烯性不飽和鍵數量的平均值為2.0(由投入量計算之值)。 After completion of the dropwise addition, the reaction was allowed to proceed for 5 hours, and after the result of IR measurement, it was confirmed that the isocyanate disappeared, and the reaction was terminated to obtain propylene glycol acrylate [PPGUA] which was obtained by using polypropylene glycol and trimethylhexamethylene diisocyanate as repeating units. And having an ethylenically unsaturated bond at both ends. The average number of ethylenically unsaturated bonds per molecule of the propylene glycol acrylate is 2.0 (calculated from the amount of input).
利用表1及表2所表示的混合比例,來調配(A)~(D)成分並攪拌混合,製備實施例1~8及比較例1~9的光硬化性樹脂組成物。此外,表1及表2中,(A)~(D)成分之數值的單位為質量份(固體成分比)。 The components (A) to (D) were blended and mixed by the mixing ratios shown in Tables 1 and 2 to prepare photocurable resin compositions of Examples 1 to 8 and Comparative Examples 1 to 9. Further, in Tables 1 and 2, the unit of the numerical values of the components (A) to (D) is a part by mass (solid content ratio).
此外,作為表1及表2中的各成分所使用之化合物如下。 Further, the compounds used as the respective components in Tables 1 and 2 are as follows.
(A1)成分 (A1) component
「合成例1」:合成例1所得之聚丁二烯甲基丙烯酸酯。 "Synthesis Example 1": Polybutadiene methacrylate obtained in Synthesis Example 1.
(A1)成分的替代化合物 Substituted compound of component (A1)
「比較合成例1」:比較合成例1所得之氫化聚丁二烯甲基丙烯酸酯。 "Comparative Synthesis Example 1": The hydrogenated polybutadiene methacrylate obtained in Synthesis Example 1 was compared.
「UC-102」:Kuraray(股)製,商品名。是下述通式(a)所表示的具有甲基丙烯醯基、聚異戊二烯衍生之結構單元的化合物(下述通式(a)中的n=2、數量平均分子量17,000)。 "UC-102": Kuraray (share) system, trade name. It is a compound having a structural unit derived from a methacryl fluorenyl group or a polyisoprene represented by the following general formula (a) (n=2 in the following general formula (a), and a number average molecular weight of 17,000).
「比較合成例2」:比較合成例2所得之氫化異戊二烯甲 基丙烯酸酯。 "Comparative Synthesis Example 2": Comparative hydrogenated isoprene A obtained in Synthesis Example 2 Acrylate.
「比較合成例3」:比較合成例3所得之丙二醇丙烯酸酯。 "Comparative Synthesis Example 3": The propylene glycol acrylate obtained in Synthesis Example 3 was compared.
(A2)成分 (A2) component
「RICON 156」:Cray Valley公司製,商品名。聚丁二烯均聚物(數量平均分子量1400)。 "RICON 156": Made by Cray Valley, the trade name. Polybutadiene homopolymer (number average molecular weight 1400).
(B)成分 (B) component
「FA-314A」:日立化成(股)製,商品名。在上述通式(1)中,R1為氫原子、R2為壬基、n的平均值為4之化合物(Mw:452)。 "FA-314A": Hitachi Chemical Co., Ltd., trade name. In the above formula (1), R 1 is a hydrogen atom, R 2 is a fluorenyl group, and a compound having an average value of n of 4 (Mw: 452).
(B)成份的替代化合物 (B) Substituting compounds
「FA-512AS」:日立化成(股)製,商品名。二環戊烯氧基乙基丙烯酸酯。 "FA-512AS": Hitachi Chemical Co., Ltd., trade name. Dicyclopentenyloxyethyl acrylate.
「FA-318A」:日立化成(股)製,商品名。上述通式1中的R1為氫原子、R2為壬基、n的平均值為8之化合物。 "FA-318A": Hitachi Chemical Co., Ltd., trade name. In the above formula 1, R 1 is a hydrogen atom, R 2 is a fluorenyl group, and the average value of n is 8 .
「ACMO」:丙烯醯基嗎啉。 "ACMO": acryloyl morpholine.
「EHA」:2-乙基己基丙烯酸酯。 "EHA": 2-ethylhexyl acrylate.
「LA」:丙烯酸月桂酯。 "LA": lauryl acrylate.
(C)成分 (C) component
「PE1」:昭和電工(股)製,商品名。下述通式(c1)所表示的季戊四醇肆(3-巰基丁酸酯)。 "PE1": Showa Denko (share) system, trade name. Pentaerythritol oxime (3-mercaptobutyrate) represented by the following formula (c1).
「BD1」:昭和電工(股)製,商品名。下述通式(c2)所表示的1,4-雙(3-巰基丁醯基氧基)丁烷。 "BD1": Showa Denko (share) system, trade name. 1,4-bis(3-mercaptobutyloxy)butane represented by the following formula (c2).
「NR1」昭和電工(股)製,商品名。下述通式(c3)所表示的1,3,5-參(3-巰基丁醯基氧乙基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮。 "NR1" Showa Denko (share) system, trade name. 1,3,5-gin(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-three represented by the following formula (c3) ketone.
(D)成分 (D) component
「TPO」:BASF公司製,2,4,6-三甲基苯甲醯基-二苯基氧化膦(最大吸收波長380nm)。 "TPO": 2,4,6-trimethylbenzimidyl-diphenylphosphine oxide (maximum absorption wavelength: 380 nm) manufactured by BASF Corporation.
對於各實施例及各比較例所得之樹脂組成物及其硬化後之透明薄片,進行以下測試。測試結果如表1及表2所示。 The resin composition obtained in each of the examples and the comparative examples and the cured transparent sheet thereof were subjected to the following tests. The test results are shown in Tables 1 and 2.
(黏度) (viscosity)
使用E型黏度計、3° cone rotor,在0.5min-1測定各實施例及各比較例所得之樹脂組成物於25℃時之黏度(mPa.s)。 The viscosity (mPa.s) of the resin composition obtained in each of the examples and the comparative examples at 25 ° C was measured at 0.5 min -1 using an E-type viscometer and a 3° cone rotor.
(相溶性) (compatibility)
將各實施例及各比較例所得之樹脂組成物填充於玻璃瓶,用目測確認相溶性,並由以下基準評估。 The resin composition obtained in each of the examples and the comparative examples was filled in a glass bottle, and the compatibility was visually confirmed and evaluated based on the following criteria.
A:樹脂組成物為透明,相溶性良好。 A: The resin composition is transparent and has good compatibility.
F:樹脂組成物為混濁,相溶性不良。 F: The resin composition was cloudy and had poor compatibility.
(波長440nm之透光率) (transmittance at a wavelength of 440 nm)
在PET(聚對苯二甲酸乙二酯)薄膜(東洋紡績(股)製,製品名「A4100」,86mm×56mm×100μm)上,滴下各實施例及各比較例所得之樹脂組成物,藉由175μm之隔片 (spacer)貼合另一枚相同PET薄膜使該樹脂組成物硬化後的膜厚為175μm。之後,由其中一片PET薄片側使用紫外線照射裝置(ORC公司製,製品名「ELM-3000B-6N」),照射2,000mJ/cm2之紫外線,使樹脂組成物硬化,來製作透明薄片(硬化物)。 The resin composition obtained in each of the examples and the comparative examples was dropped on a PET (polyethylene terephthalate) film (manufactured by Toyobo Co., Ltd., product name "A4100", 86 mm × 56 mm × 100 μm). The film thickness of the resin composition after hardening of the same PET film by a spacer of 175 μm was 175 μm. Then, an ultraviolet ray irradiation device (product name "ELM-3000B-6N" manufactured by ORC Co., Ltd.) was used for one of the PET sheets, and ultraviolet rays of 2,000 mJ/cm 2 were irradiated to cure the resin composition to produce a transparent sheet (cured material). ).
將兩層PET作為透光率的基準線,從所得之三層積層體(PET薄膜/硬化物/PET薄膜)上剝除PET薄膜,將殘留硬化物的波長440nm之透光率,用分光光度計(島津製作所(股)製,製品名「UV-2400PC」)測定。 Using two layers of PET as the reference line of light transmittance, the PET film was peeled off from the obtained three-layer laminate (PET film/cured material/PET film), and the transmittance of the residual cured product at a wavelength of 440 nm was used for spectrophotometry. (Measured by Shimadzu Corporation (stock), product name "UV-2400PC").
又,對於所測定之440nm之透光率的數值,由以下基準評估。 Further, the value of the measured transmittance at 440 nm was evaluated by the following criteria.
A:波長440nm之透光率為98%以上,透光率良好。 A: The light transmittance at a wavelength of 440 nm is 98% or more, and the light transmittance is good.
F:波長440nm之透光率未滿98%,透光率低劣。 F: The light transmittance at a wavelength of 440 nm is less than 98%, and the light transmittance is inferior.
(折射率) (refractive index)
在PET(聚對苯二甲酸乙二酯)薄膜(東洋紡績(股)製,製品名「A4100」,86mm×56mm×100μm)上,滴下各實施例及各比較例所得之樹脂組成物,藉由350μm之隔片貼合另一枚相同PET薄膜使該樹脂組成物硬化後的膜厚為350μm。之後,由其中一片PET薄片側使用紫外線照射裝置(ORC公司製,製品名「ELM-3000B-6N」),照射2,000mJ/cm2之紫外線,使樹脂組成物硬化,來製作透明薄片(硬化物)。 The resin composition obtained in each of the examples and the comparative examples was dropped on a PET (polyethylene terephthalate) film (manufactured by Toyobo Co., Ltd., product name "A4100", 86 mm × 56 mm × 100 μm). The film thickness of the resin composition after curing of the same PET film by a separator of 350 μm was 350 μm. Then, an ultraviolet ray irradiation device (product name "ELM-3000B-6N" manufactured by ORC Co., Ltd.) was used for one of the PET sheets, and ultraviolet rays of 2,000 mJ/cm 2 were irradiated to cure the resin composition to produce a transparent sheet (cured material). ).
從所得之三層積層體(PET薄膜/硬化物/PET薄膜)上剝除PET薄膜,將殘留硬化物在25℃、波長589nm之折射率,用ABBE折射率計(Atago(股)製,製品名「DR-M2」) 測定。 The PET film was peeled off from the obtained three-layer laminate (PET film/cured material/PET film), and the refractive index of the residual cured product at 25 ° C and a wavelength of 589 nm was measured by an ABBE refractometer (Atago). Name "DR-M2") Determination.
(頻率1MHz時之介電常數) (Dielectric constant at a frequency of 1 MHz)
在離型PET薄膜上,放上直徑50mm、膜厚2mm之矽膠圓形框,在其中填充各實施例及各比較例所得之樹脂組成物,並在其上覆蓋PET薄膜,用紫外線照射裝置(ORC公司製,製品名「ELM-3000B-6N」),照射1J/cm2之紫外線,使樹脂組成物硬化,來製作透明膜(硬化膜)。將該硬化膜的頻率1MHz時之介電常數,用介電質測定用專用電極「HP16451B」及「HP4275A」(製品名,惠普公司製Precision LCR Meter)測定。 On the release PET film, a silicone circular frame having a diameter of 50 mm and a film thickness of 2 mm was placed, and the resin composition obtained in each of the examples and the comparative examples was filled therein, and the PET film was covered thereon, and an ultraviolet irradiation device was used. The product name "ELM-3000B-6N" manufactured by ORC Co., Ltd. was irradiated with ultraviolet rays of 1 J/cm 2 to cure the resin composition to produce a transparent film (cured film). The dielectric constant at a frequency of 1 MHz of the cured film was measured using special electrodes "HP16451B" and "HP4275A" (product name, Precision LCR Meter manufactured by Hewlett-Packard Co., Ltd.) for dielectric material measurement.
(遮光部硬化寬度) (shading portion hardening width)
將各實施例及各比較例所得之樹脂組成物,滴下於16公分見方之玻璃基板上,藉由175μm之隔片貼合另一枚16公分見方之玻璃基板使膜厚為175μm。之後,由其中一片玻璃基板側使用紫外線照射裝置(ORC公司製,製品名「ELM-3000B-6N」),照射2,000mJ/cm2之紫外線,使樹脂組成物硬化,來製作測試片(硬化物)。此外,此時在照射紫外線之玻璃基板單側,用波長200~800nm之透光率為0的黑陶瓷,來形成8cm×16cm之遮光部,並設置於樹脂組成物側之面。 The resin composition obtained in each of the examples and the comparative examples was dropped on a glass substrate of 16 cm square, and another 16 cm square glass substrate was bonded to a 175 μm film to have a film thickness of 175 μm. Then, an ultraviolet ray irradiation apparatus (product name "ELM-3000B-6N" manufactured by ORC Co., Ltd.) was used to irradiate ultraviolet rays of 2,000 mJ/cm 2 to cure the resin composition, thereby preparing a test piece (cured material). ). Further, at this time, a black ceramic having a light transmittance of 0 at a wavelength of 200 to 800 nm was formed on one side of the glass substrate irradiated with ultraviolet rays to form a light-shielding portion of 8 cm × 16 cm, and was provided on the surface of the resin composition side.
之後,剝除測試片單測的玻璃,將遮光部部分的完全成膜之樹脂組成物,用游標卡尺測定寬度,將該數值作為遮光部硬化寬度。該數值越大,則表示在遮光部中的硬化性越優異。 Thereafter, the glass of the test piece was peeled off, and the resin composition of the fully formed film portion of the light-shielding portion was measured with a vernier caliper, and this value was defined as the light-shielding portion hardening width. The larger the value, the more excellent the hardenability in the light shielding portion.
表1
表2
由表1可知,實施例1~8的光硬化性樹脂組成物,具有適當黏度,相溶性亦良好,遮光部硬化寬度亦在40mm以上,並且在遮光部中的硬化性優異。又,該樹脂組成物之硬化物,其透光率、折射率、及介電常數皆良好。 As is apparent from Table 1, the photocurable resin compositions of Examples 1 to 8 have an appropriate viscosity, good compatibility, and a light-shielding portion hardening width of 40 mm or more, and are excellent in hardenability in a light-shielding portion. Further, the cured product of the resin composition had good light transmittance, refractive index, and dielectric constant.
另一方面,由表2可知,比較例1~4、6~9的光硬化性樹脂組成物,其遮光部之硬化無法充分進行。又,比較例5~9的光硬化性樹脂組成物的結果,其相溶性差,由該樹脂組 成物所得之硬化物的透光率亦低劣。 On the other hand, as is clear from Table 2, in the photocurable resin compositions of Comparative Examples 1 to 4 and 6 to 9, the curing of the light-shielding portion was not sufficiently performed. Further, as a result of the photocurable resin compositions of Comparative Examples 5 to 9, the compatibility was poor, and the resin group was The light transmittance of the cured product obtained by the product is also inferior.
本發明之光硬化性樹脂組成物,其在遮光部中的硬化性優異,具有適當黏度,且相溶性良好。因此,本發明之光硬化性樹脂組成物,可適用於影像顯示用裝置中,具有沿著外周邊的遮光部之保護面板與影像顯示元件等之間隙的空間部分的填充材料。 The photocurable resin composition of the present invention is excellent in curability in a light-shielding portion, has an appropriate viscosity, and has good compatibility. Therefore, the photocurable resin composition of the present invention can be suitably used in a video display device, and has a filling material in a space portion of a gap between a protective panel and a video display element such as a light shielding portion on the outer periphery.
1A‧‧‧液晶顯示用裝置 1A‧‧‧LCD display device
1‧‧‧影像顯示元件 1‧‧‧Image display components
10‧‧‧液晶顯示單元 10‧‧‧LCD unit
20、22‧‧‧偏光板 20, 22‧‧‧ polarizing plate
32‧‧‧樹脂層 32‧‧‧ resin layer
40‧‧‧保護面板 40‧‧‧Protection panel
41‧‧‧遮光部 41‧‧‧Lighting Department
50‧‧‧背光系統 50‧‧‧Backlight system
P‧‧‧遮光部的背側部分 P‧‧‧Back side of the sunscreen
Q‧‧‧透光部 Q‧‧‧Transmission Department
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JP6225611B2 (en) * | 2013-09-24 | 2017-11-08 | 日立化成株式会社 | Photo-curable resin composition, image display device and manufacturing method thereof |
JP2015172176A (en) * | 2014-02-18 | 2015-10-01 | 日立化成株式会社 | Photocurable resin composition, photocurable light-shielding coating and light leakage prevention material using the composition, liquid crystal panel, liquid crystal display and photo-curing method |
JP6476660B2 (en) * | 2014-08-29 | 2019-03-06 | 日立化成株式会社 | Photocurable resin composition, photocurable light-shielding coating material using the same, liquid crystal display panel, and liquid crystal display device |
TWI673323B (en) * | 2014-12-22 | 2019-10-01 | 日商昭和電工股份有限公司 | Active energy ray hardening composition and use thereof |
JP6675380B2 (en) * | 2015-03-12 | 2020-04-01 | ナミックス株式会社 | Resin composition, adhesive, and sealant |
KR102269289B1 (en) * | 2018-01-11 | 2021-06-25 | 주식회사 엘지화학 | Adhesive composition, adhesive film and touch screen panel comprising the adhesive film |
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