TW200900816A - Hardening resin composition for liquid crystal sealing and manufacturing method for liquid crystal display panel using the same - Google Patents

Abstract

This invention relates to a hardening resin composition for liquid crystal sealing which can become an liquid crystal seal agent. The hardening resin composition for liquid crystal sealing includes a acrylic acid resin and/or a (meth)acrylic denaturation epoxy resin having at least one epoxy group and one (meth)acrylic group in one molecule, a heat radical polymerization initiator and a filler, which is characterized by that the viscosity measured by an E type viscometer at 25 degrees Celsius and in 1. 0rpm is 50-500Pa*s and the viscosity measured by an E type viscometer at 80 degrees Celsius and in 1. 0rpm is more than 500Pa*s. Because the cure rate of the hardening resin composition for liquid crystal sealing is fast, the leak of the liquid crystal and the pollution of the liquid crystal can be controlled. Therefore, high quality liquid crystal display panels can be produced with high productivity be using the liquid crystal seal agent which consists of the hardening resin composition for liquid crystal sealing.

Description

200900816 IX. Description of the invention: [Technical field to which the invention pertains] The use of a curable resin composition and the use thereof [Prior Art] ^ In recent years, liquid crystal display panels have been

: Special: 7 is used as each of the "electronics" represented by a mobile phone: ΐ: ===== Device: It has a liquid crystal density to display an image. 】 夜 夜 调 调 调 调 调 调 调 调 调 调 调 调 调 调 调 调 调 调 调 调 调 调 调 调 调 调 调 调 调 调 调In the liquid crystal injection technique, a liquid crystal sealing agent is applied onto any of the two substrates of the first base to form a frame, and then the frame-shaped liquid crystal sealing agent is dried by a pre-hardening treatment. Here, a cutout portion which becomes a liquid crystal injection port is previously provided on the portion of the frame. Next, after the two substrates are opposed to each other, they are hot-pressed, whereby the substrates are brought together. Thereby, a unit for enclosing the liquid crystal is formed between the two substrates. Then, the liquid crystal is injected into the empty cell from the liquid crystal injection port under vacuum, and then the liquid crystal injection port is sealed with a liquid crystal sealing agent or the like to thereby manufacture a liquid crystal display panel. For the liquid crystal sealing agent for liquid crystal injection, for example, a thermosetting liquid crystal sealing agent containing an epoxy resin as a main component (hereinafter, simply referred to as a thermosetting sealing agent) has been proposed (for example, refer to International Publication No. 2004/039885). 6 200900816 27285pif However, in recent years, with the small size, thinness, and high quality of electronic equipment, the demand for liquid crystal display panels has increased remarkably. Therefore, in the field of manufacturing liquid crystal display panels, there is a strong desire for improvement in productivity, including high quality of products or shortened manufacturing time. However, in the above liquid crystal injection technique, it is considered to have a low productivity due to the long injection time of the liquid crystal and the necessity of heat treatment at 120 to 15 (temperature of TC for several hours) in order to cure the thermosetting sealant. In view of the above, liquid crystal dropping technology has recently attracted attention as a manufacturing method of a liquid crystal display panel which can improve productivity. Liquid crystal dropping technology generally consists of the following steps. First, by a dispenser (dispenser) Or screen printing or the like, applying a liquid crystal sealing agent to any one of the two substrates constituting the liquid crystal display panel to form a frame filled with liquid crystal. Then, an appropriate amount of liquid crystal is dropped into the frame. Two substrates are superposed under a high vacuum through an uncured liquid crystal sealing agent, and the two substrates that have been overlapped are returned to atmospheric pressure to bond the substrates to each other, and then the liquid crystal sealing agent is cured. A liquid crystal display panel in which liquid crystal is sealed between two substrates is produced. Further, in the present invention, a frame made of a liquid crystal sealing agent is used. In the liquid crystal dropping technique, in order to shorten the curing time of the liquid crystal sealing agent, the liquid crystal sealing agent is irradiated with ultraviolet rays or the like by using a light and a thermosetting liquid crystal sealing agent. The liquid crystal sealing agent is temporarily hardened, and then post-hardened by heating (for example, refer to Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei. No. Hei. No. 2-214626). Compared with the prior liquid crystal injection technology u 7 200900816, the liquid crystal can be sealed between the substrates in a shorter time, and the hardening time of the liquid crystal sealing agent is shortened, thereby improving productivity. Therefore, the liquid crystal dropping technology has gradually become the recent technology. The mainstream of the manufacturing method of the liquid crystal display panel. However, as the wiring of the small panel mounted on the mobile phone becomes more complicated, the seal pattern and the wiring are overlapped with each other, and the light-shielding portion where the light cannot be directly irradiated is easily generated on the seal pattern. However, since the hardening of the liquid crystal sealing agent is insufficient in the light shielding portion, it is heated by heating. When the post-hardening is performed, the liquid crystal intrudes into the sealing pattern, causing a large amount of occurrence of the following: the sealing pattern is deformed, or the liquid crystal leaks through the sealing pattern to cause leakage of the liquid crystal. If the liquid crystal leaks, the display characteristics of the liquid crystal display panel may significantly decrease. Moreover, if the liquid crystal is in contact with the uncured liquid crystal sealing agent, the hardened liquid crystal sealing agent may infiltrate into the liquid crystal, which may easily cause contamination of the liquid crystal, and liquid crystal contamination may also cause display characteristics of the liquid crystal display panel. Significantly lower t is therefore a 'liquid crystal sealant that can inhibit liquid leakage or liquid crystal contamination.

In the liquid crystal sealing agent which can improve the liquid crystal leakage, for example, a curable resin composition for a device is proposed, and the viscosity under the measurement condition of 25 ° C and h 疋 using the e-type adhesive is 200 2 . 〇PaV:: 'The viscosity under the measurement conditions of 8〇t, 1,0 rPm is F 八~ (for example, refer to the Japanese Special Edition 2_-308811 Light Patent Special Opening · · ). A liquid crystal sealing agent which can be sufficiently cured, for example, a liquid crystal 8 200900816 27285pif dense, which contains a photocurable resin, a photoradical polymerization initiator, and a chalk having a disulfide bond (disulfide bond). l 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基Low level of liquid crystal sealing agent, proposed to have __ kind of i molecule = bond functional group amount is greater than or equal to 3.5 χ 1 〇, liquid crystal sealing with thermal hardening

Where: ^ The amount of hydrogen bond functional groups in one molecule of the document towel is defined by the number of hydrogen bonds of the hydrogen bond, and since the value of the resin is greater than or equal to 3, the resin has a low affinity for the crystal, so it can be lowered. It is a clever and dyeable liquid crystal. SUMMARY OF THE INVENTION However, in recent years, with the increase in the amount of information, the high > month=ization of the liquid crystal display panel has progressed further, and the ratio of the light-shielding portion of the liquid crystal age panel is increased by π. The prior art disclosed in each of the above documents cannot sufficiently suppress deformation of the sealing portion at the time of heat curing or leakage of liquid crystal to the sealing portion. In addition, a liquid crystal sealing agent using a high activation energy generated by photo radicals as shown in Japanese Laid-Open Patent Publication No. 2006-030481 is difficult to make a liquid crystal sealing agent without leaving an uncured portion under the current high definition. hardening. In the case where the liquid crystal sealing agent which reduces the light-shielding portion is not hardened, the following method or the like can be considered, and the sealing pattern is designed in consideration of the irradiation of light; 2) when the liquid crystal sealing agent is hardened by the liquid crystal dropping technique Ultraviolet radiation was changed to heating. However, the method of 1) imposes limitations on the panel design and is therefore poor. In addition, since the photocurable liquid crystal has been used for a long time, there is a problem in terms of equipment cost or energy cost for manufacturing the ultraviolet ray. On the other hand, the method of 2) _ the reaction is slower than the reaction of the light, and it is easy and low in the domain. Therefore, it has been difficult to solve the problem of liquid crystal leakage problems such as the use of the liquid crystal of the thermosetting tree. ... 廿 Based on the above, the inventors of the present invention conducted a marrow study on the shallow leak resistance agent. The result is: 1) the viscosity of the sealing agent during thermosetting, 2) the liquid crystal sealing domain corresponding to the radical chain transfer agent or liquid crystal sealing agent: the remainder of the hardening property, = or leakage resistance influences. In addition, in the above preliminary study, the present inventors have studied the resistance of the liquid crystal sealing agent disclosed in Japanese Patent Publication No. 813, No. 813, from (4) Its resistance to $ leak is not sufficient. Yu 彳 =; resin coffee ^ full. Research% of the sealant's resistance to leakage is not

In view of the above-mentioned problem, the purpose of the present invention is to provide a state in which the liquid crystal is prevented from leaking, the liquid crystal is smeared, the hexagram-I, and the liquid crystal sealing is used to form a productive state. Plate 3 = group that remains high ί发:=ί=Γ::: The result is focused on the resin composition. That is, the viscosity of the resin composition of the above-mentioned course was completed, and the present invention was solved by the composition of the curable resin for liquid crystal sealing of the present invention 10 200900816 27285pif.匕 匕 ] 种 种 硬化 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶The epoxy group, the (fluorenyl) acrylonitrile group, the thermal self-polymerization initiator, and the filler, and the curable composition for liquid crystal sealing are 25 measured by an E-type viscosity meter. 〇, the viscosity at 1.0 rpm is 0 Pa s~500 Pa.s, and the viscosity at 80 ° C ' 1_0 rpm is greater than 500 pa. s. [2] The curable resin composition for liquid crystal sealing according to [1], wherein the upper primary particle diameter (average primary is equal to 1.5 and the specific surface area (speciflc smface rainbow (5)) is ^ 叻 / g 2 5 〇〇 m 2 /g 'and 100 parts by weight of the total of the acrylic resin and the (meth)acrylic modified epoxy resin, the content of the filler is 〜50 parts by weight of the protective portion, Viscosity at 25 〇c, 〇.5 rpm measured by an E-type viscometer] / [Temperature index defined by an E-type viscometer at 25 ((:, viscosity at 5.0 rpm)]硬化tr〇py index) is a hardenable resin composition for liquid crystal sealing according to [1] or [2], wherein the thermal radical polymerization is carried out at a certain temperature. When the initiator is subjected to a thermal decomposition reaction at a temperature of one hour, the temperature of the thermal radical polymerization initiator is reduced to half, and the temperature of the thermal radical polymerization initiator defined by the above-mentioned thermal radical polymerization initiator is 4 (TC to 8 〇t). [4] A curable resin composition for liquid crystal sealing, which contains a molecule capable of undergoing radical polymerization _•carbon double The radical hardening of the bond: 200900816 A resin, a thermal radical polymerization initiator, a radical chain transfer agent, and a filler. [5] The curable resin composition for liquid crystal sealing according to [4], wherein the radical [6] The sulphuric acid resin composition for liquid crystal sealing according to [4] or [5], wherein the thiol group as the radical chain transfer agent has a number average molecular weight of 400 〜 2000 secondary thiols.

[7] The curable resin composition for liquid crystal sealing according to any one of [4], wherein the curable resin composition for liquid crystal sealing is 25 measured by an E-type viscosity meter. (:, the viscosity at 1.0 rpm is 5 〇Pa.s~5〇〇Pa.s, and the viscosity at 80 ° C, l.Orpm is greater than 5 〇〇 Pa.s. [8] - for liquid crystal sealing a curable resin composition comprising a resin composition having a carbon-carbon double bond, a functional group, and an epoxy group which can be freely bonded, a hot free-knit starter, and a filler; the above resin composition Containing two or more resins selected from the group consisting of: (1A) a radical reactive resin having a bond functional group and two carbons capable of undergoing radical polymerization in a ruthenium molecule The double bond and the above hydrogen bond functional group amount is 1.5 x 1 〇 · 3 mc) i / g 〜 6 Gxl (r3 mGl / g, a radical reactive tree, which has a hydrogen bond functional group, epoxy in the molecule a base, and a carbon fiber which can be freely bonded, and the above hydrogen bond ruthenium base amount is LOxKT moi/g~5.0xl0-V〇1/g, and (lc) epoxy resin, which is in the inner t has an epoxy group but does not have a carbon-carbon double bond capable of undergoing radical polymerization and/, a softening point (S〇ftenmgp〇int) measured by a ball and ball method (ringandballmeth〇d) is greater than or equal to 4〇 , and the weight of the lion is delayed; the amount of hydrogen bond in the above resin composition is 〇: 12 200900816 27285pif Γ =: 6. ° Γ _ mo 】 / g; the amount of epoxy groups in the above composition is 1.0 [10] The curable resin composition for liquid crystal sealing according to the above [8], wherein the hydrogen bond functional group in the resin composition is a hydroxyl group. [10] The curable resin composition for liquid crystal sealing according to [8] or [9] wherein the radical reactive resin of the above (1A) is represented by the following formula (10) or the formula (a2) Resin.

(al) In the above formula (al), ]I, R3 and R4 each independently represent a hydrogen atom or a methyl group; and independently represent a hydrogen atom, and the carbon number is 丨~斗An alkyl group or an olefin group having 1 to 4 or an alkyl group having a carbon number of 4; 11 representing an integer of 1 to 4; and 1 representing an integer of 1 to 4;

General formula (a2) 13 200900816 / t l In the above formula (a2), R5, R_6, R7, and Κ8 each independently represent a hydrogen atom or a fluorenyl group;

Rq each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an allyl group, a hydroxyalkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; and r represents 1 to 4; Integer; ρ represents an integer from 1 to 4. [11] The curable resin composition for liquid crystal sealing according to any one of [10], wherein the radical reactive resin of the above (1A) is represented by the following formula (a3) or A4) Resin represented.

(general formula (a3) in the above formula (a3),

Ri and R2 each independently represent a hydrogen atom or a fluorenyl group;

Rm* independently represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, an allyl group, a hydroxyalkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; η represents 1 to 4; An integer of - is an organic group represented by -CH2-, -C(CH3)2-, -S02-, or

General formula U4) 14 200900816 27285pif In the above formula (a4), R5 and R6 each independently represent a hydrogen atom or a fluorenyl group. [12] The curable resin composition for liquid crystal sealing according to [8], wherein the viscosity of the liquid BB sealing curable resin composition measured at 25X:, 1.0 rpm measured by an E-type viscosity meter is 5〇Pa.s~5〇〇Pa.s, and the viscosity at g0 °C, l.Orpm is greater than 5〇〇Pa.s. [13] The liquid crystal enthalpy-curable resin composition according to [8], wherein the liquid crystal (IV) hardenable resin composition further contains a radical bond agent. [14] The curable resin composition for liquid crystal sealing according to [13], wherein the viscosity of the hard-recorded resin residue for liquid crystal sealing is measured at 25 C and 1.0 rpm as measured by the E-type reduction. 5〇pa s~5〇〇pa s, and the viscosity at g〇C, l.Orpm is greater than 5〇〇Pa s. According to the method for manufacturing a liquid crystal display panel for manufacturing a liquid crystal display panel of the present invention, a liquid crystal melamine & ya composition is used to bond two substrates facing each other. In the manufacturing method of the second wide panel, the manufacturing step of the liquid crystal display panel is a step of preparing a first substrate, and the first substrate or the frame-shaped display region is sealed by the above [1], [4], and region. a step of surrounding the first substrate and the opposite direction of the first substrate in the display region surrounding the pixel array-based hardened state by the hardening tree frequency, or by moving it to the opposite direction; Further, the liquid crystal sealing tree 15 200900816 is subjected to a step of hardening the fat composition. (4) A method for producing a high-quality liquid crystal display panel in a state in which the liquid crystal contamination panel can be produced by using a curable resin composition for suppressing liquid (4) leakage and liquid crystal contamination, and the like. (5) Method for producing a high-quality liquid crystal display panel in a state of productivity [Embodiment] Detailed description. In the following description, the numerical range is defined by "~", but the "~" of the present invention includes the boundary value (b_dary, mi Γ10^100-ft, the so-called "liquid crystal sealing", meaning "for sealing liquid crystal" "In the present invention, the sealing liquid is sealed in a certain space", and the "curable resin composition for liquid crystal sealing" in the present invention is generally referred to as "liquid crystal sealing". Agent I is a shy 曰 ρη ", - sh 玎 」 t t t t 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶In the liquid crystal sealing agent, a liquid crystal sealing agent which can be used for a liquid crystal dropping technique is sometimes referred to as a "liquid crystal sealing agent for liquid crystal dropping technology" in the present invention. In the following description, the "curable resin composition for liquid crystal sealing" is referred to as "composition material", "liquid crystal sealing agent" or "sealant". The characteristics of the curable wax composition for liquid crystal sealing are It contains (1) acrylic wax, and/or (2)-molecule having at least 1 chest county base and (methyl) propyl-fine (methyl) propylene glycol acid modified 16 200900816 27285pif epoxy resin (3) a thermal radical polymerization initiator, and (4) a filler; the liquid crystal rhyme is composed of a curable resin (4). The viscosity at 25 C I0 rPm measured by an E difficulty meter is 50 Pa.s to 500 Pa.s, And the viscosity at 80 C l.0rPm is greater than 5 〇〇 pa.s. In the present invention, acryl, methacrylic acid (methacr state is also called (meth) propyl hydrazine Further, the sclerosing tree test composition for liquid crystal sealing of the present invention having the above characteristics is also referred to as "liquid crystal (four) curable resin composition. "No I" or "resin composition I". The above viscosity is an E-type rotary viscometer such as a digital rheometer manufactured by BROOKFIEL (Model: Dn_m ULTRa), and a CP-52 having a radius of i2 mm and 3 is used. The cone-plate type sensor (c〇ne and plate =), the rotation speed is set to 1 〇 - and the measurement is performed. At this time, the square line is measured, so-called 25 ° CT Viscosity refers to the viscosity obtained by placing the liquid crystalline inert resin composition 1 under the pit for 5 minutes. The viscosity at 8 〇 is the value of the J to the viscometer cup. The rate of rise and fall of °c/min is H 8G C, and then measured by the method of _ degrees. Knife (four) 冉 above fans

Method). The FF is measured by the parallel plate method using a rotor _ (coffee; J Λ upper-type rotary viscometer:: the measurement limit is about 780 Pa. S. " For example, RheoStress RS150 17 200900816 (manufactured by HAAKE) can be used. The viscoelastic tears are made by the quasi-method. The material is based on the standard h/ί crystal seal of the model. The hard resin composition 1 is characterized by a viscosity of 5 GPa.s at 25 C, . rpm~ 5G()p 7, τ* aa taste i· ώ:丄(λλ η Λ b C N1.0 rpm

The viscosity is greater than 500 Pa.s; more preferably, the viscosity is 100 Pa.s to 400 pa.s. In this recording, the composition of S at the rpm is applied as a liquid crystal seal 1 to the wire, and since (4) the bubbles contained in the recording are provided, a high-quality crystal display panel can be provided. Further, the thickness of the composition I for the liquid crystal sealing is such that the viscosity at 8 〇t and 1. 〇 rpm is larger than _ pa s . Usually, when the thermosetting resin is cured by heating, the viscosity of the resin increases again as the curing reaction progresses. = Often, when manufacturing a liquid crystal display panel, the curing temperature of the liquid crystal sealing agent is about 8 〜 to 150 C. As described above, if the viscosity of the composition in the hardening step is excessively lowered, problems such as liquid crystal leakage occur. In order to prevent liquid crystal leakage (to improve leakage resistance), an effective method is to suppress a decrease in viscosity of the composition at the time of heat hardening. In order to suppress the decrease in the viscosity of the composition during the hardening, it is effective to carry out the hardening reaction of the composition before the viscosity reduction occurs, and to increase the viscosity of the composition. In addition, in order to suppress liquid crystal leakage, the viscosity of the composition at 8 叱 and 1 G is 5 〇〇 Pa*s as a standard. Therefore, the resin composition of the present invention is as follows: • The composition design is carried out: the hardening of the composition is promoted by using a thermal radical polymerization initiator having an hour-half-life temperature within a predetermined range as described below. Thereby, the viscosity of the composition at 80 ° C and 1.0 rpm 18 200900816 27285pif is more than 500 Pa s ', and the viscosity of the composition can be made before the viscosity is lowered. Therefore, the viscosity at the time of heat curing can be suppressed from being lowered. Here, in view of suppressing the decrease in the viscosity of the object at a lower level, the viscosity at (10) c above is preferably 1〇3pa.s~1〇9pa.s, more preferably i〇3pa. s~10' Pa.s. Further, the viscosity of the curable resin composition j for liquid crystal sealing is [Yu Nai, viscosity at 0/rpm; j/[ at 25.黏, 5. 〇 的 viscosity] The defined touch η ί index is u ~ 5.0, preferably 1.2 ~ 2.5. The so-called thixotropic index, 疋 refers to the lower shear rate (shear vek) dty) _ the viscosity of the fish determined by the shear rate measured by the shear rate. If the ratio is high, the fluid of the resin composition J will flow at a high viscosity at a low shear rate and will flow at a low viscosity at a high shear rate. When the liquid crystal display panel is manufactured, in the step of coating the liquid crystal sealing agent on the substrate: in the case where the liquid crystal sealing agent is in a high shearing speed, and then the substrate is superposed and post-hardened, the liquid crystal sealing agent is in the shearing The rate of r-speed is only ΐ. Here, in the step of applying a liquid crystal sealing agent on a substrate (the cutting speed region), it is necessary to easily apply the film, and it is easy to defoam the liquid crystal sealing agent. Therefore, it is preferred that the liquid crystal sealing agent has a low viscosity. Further, in the hardening process (low shear region), as described above, liquid crystal leakage does not occur, and therefore it is preferred that the liquid crystal sealing agent has a high viscosity. In the case of the liquid crystal sealing agent, the coating property of the liquid crystal sealing agent for liquid crystal sealing is good in defoaming property and reliability, and the thixotropic index is set to the above range. The composition I is characterized in that (1) an acrylic resin, and/or a (meth)acrylic modified epoxy resin having at least one epoxy group and (meth)acrylic acid in 19200900816 As a base resin, the pot contains a free silk starter and (4) a filler; and the money composition has an unhardened state agent (curable resin) and a hardener (hard) and a so-called one-liquid hardening_fat composition - Liquid-hardening tree = (1) Acrylic resin olefin strontium 酉 是 是 是 丙 是 液 液 液 液 液 液 液 液 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是 是Vinegar and/or methacrylic polyethylene glycol or 4, an amphoteric polymer. Examples of these include the following: methacrylic acid ester; etc. Diacrylate and/or di- or dimethacrylate; The acrylate and/or addition of the di-diester acid ester to the di-propylene S3 ergo of the neopentyl lysine (neopentyl gly C〇i) diol (bisPhen〇1 A彳 or Methyl propyl acrylate; diol $ _ ^ obtained in 1 mole of bisphenol into 2 moles of ethylene oxide or propylene oxide ear , - olefinic acid and / or dimethyl propyl sulphate S; in 1 epoxiconate and ^ greater than the molar epoxy acetonitrile or propyl phthalate; in, alcohol - or Diacrylate and/or di- or trimethyl epoxiconate or diol diacrylate obtained by adding 2 mol of dimethyl acrylate acid to the double age A of Λmol And/or field, bis(2-hydroxyethyl)isocyanate triacrylate and / 20 200900816 27285pif or tridecyl acrylate; trimethylolpropane triacrylate and / or trimethacrylic acid S, or its Polymer; pentaerythritol triacrylate acrylate and/or tridecyl acrylate, or oligomer thereof; polyacrylic acid vinegar and/or polymethacrylate of dipentaerythritol; tris(propylene oxyethyl) isocyanate; Ester-modified tris(propylene oxyethyl) isocyanate; caprolactone modified tris (methyl propylene)

醯 oxyethyl)isocyanate; polyacrylate and/or polydecyl acrylate of alkyl modified dipentaerythritol; polyacrylate and/or polymethyl propyl phthalate of caprolactone modified dipentaerythritol; Neopentyl glycol neopentyl glycol diacrylic acid brewing and / or dimercapto acrylate; caprolactone modified hydroxypivalic acid neopentyl glycol diendoic acid 0 曰 and / 驭 di T acrylate; Ethylene oxide modified phosphoric acid acrylate vinegar and / or dimethacrylate; ethylene oxide modified alkylated phosphoric acid acrylate and / or dimethacrylate; neopentyl glycol, trihydroxy decyl propane, An oligomeric polyacrylate and/or an oligomeric methacrylate of pentaerythritol. In addition, the specific examples of the above-mentioned acrylic tree include: an epoxy resin (CreS〇lnCm) lac) type epoxy resin, a benzene oligo oliac, an oxygen resin, and a double-type A-type epoxy resin. Resin, double-type f-type epoxy resin, triphenyl sinter-type epoxy resin triphenyl _ epoxy _ purpose, simmering type epoxy resin, resin, fresh yoghurt = ^ diene type epoxy should The obtained epoxy resin is completely (a = base and (: base) acrylic acid anti-monthly tr acrylic resin is preferably made by the water washing method or the like to make the acrylic acid resin of the present invention, more than # Μ θ U , ~ 2 _ Within the range, and ^ is its number average molecular weight in the theoretical solubility parameter of ed〇rs 200900816 (S〇M^ty]parameter '叩 value) at 1〇〇(五)/cm3广~咖(cal/cm) 0 la In this case, the acrylic resin and the diffusibility are lowered. Therefore, the liquid crystal sealing agent containing the resin can provide a liquid crystal display panel having excellent display characteristics, and (4) preferably = (4) the compatibility of the epoxy resin is also good. Therefore, the sealant. The above number average molecular weight, for example, can be determined by GPC > gel permeation chromatography ^ The ethylene is determined as a standard. The calculation parameter of the solubility parameter (sp value) is preferably the base 2, and the '^ is the one (see 曰 接着 学会 学会, vol22, = 986) (53) (566) Wait). The reason is in the density value, so it can be transferred to the anvil head Yamada%. This theoretical cloud solubility parameter can be based on the solution parameter. The sp value of the above Μ(10) = (ΣΑεΙ/ΣΔνΙ) 1/2

/, Σ Σ ε Ι - (δ η - RT), the sum of the 2 △ 莫 耳 容量 容量 容量 、 、 、 、 、 ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ Mixed moon: 'may also be a combination of several kinds of the above acrylic resins in the mouth of each of the acrylic styrene monomer and / or mercapto propyl 22 200900816 27285pif oleic acid vinegar monomer, or the like of the oligomer Within the range of the sum of the percentages of the moles. The number of average knives is 3〇〇~2〇〇〇 and the theoretical dissolution of Fed〇rs

^f〇(Cal/-3) 1/2-13.0 (Example of calW acrylic resin, quaternary alcohol tetra-acid) (the number average molecular weight is 352, and the sp value is 12.1). A (meth)acrylic acid-modified epoxy resin having one or more epoxy groups and a fluorenyl fluorene group, each having one or more epoxy groups in the molecule 0 propylene-based (meth)acrylic acid-modified epoxy resin (also modified as epoxy resin). Acryl sulfhydryl and epoxy compound. In-situ 1, (methyl) A resin obtained by reacting a bis-oxygen resin or a dilute acid 31" = a Wei resin with a (meth) acid or a methyl propyl group under an inert catalyst. Examples of the epoxy resin of the raw material include bis (4) oxyester oxy-resin, triphenyl sulphate, milk sap, two sinter-type cyclopentane (tetra) resin, triphenyl _ epoxy resin, two: _ & _ Lipid, biphenyl type epoxy resin, etc. A s-energy epoxy resin and acrylic acid having a ratio of oxy group and acrylic acid of approximately 1:1 with two ring-shaped resin, Wei F-type epoxy resin and the like. React得得23 200900816 'The above epoxy resin is preferably purified by molecular steaming method, /month/no go, etc. f A is changed from f to f lion in Shuqi (4) both epoxy and r ^ '. Base, and therefore in the curable resin composition for liquid crystal sealing): The olefinic resin is excellent in compatibility with the following (6) epoxy resin. Since t provides a glass transition temperature (? transition temperature, τ ) The cured product of the material. Since the cured product of the composition is excellent in the endurance of the cured product and the substrate, a high-quality liquid crystal display panel can be provided. In the middle of the '(1) acrylic resin and (2) modified ring The oxy-resin may be used instead of: 〇 only: (1) acrylic resin is used instead of (2) modified epoxy resin; or b) only modified epoxy resin is used instead of (1) acrylic resin In this case, in the case of a, it is possible to provide a curable tree for liquid crystal sealing which is excellent in resistance to leakage (in the case of b), by (2) modifying epoxy resin and _hard_ A suitable combination can provide a curable resin composition for liquid crystal 1 having a high strength. In the invention, in the characteristics of the liquid crystal sealing agent, the case where the liquid crystal sealing agent and the substrate to be bonded are as high as the bonding strength of the substrate is referred to as excellent reliability. Further, '1) acrylic resin and (2) modified ring may be used in combination. Oxygen resin. The mixing ratio of each resin is preferably by weight (1) acrylic resin: (2) modified epoxy resin = 1 〇 ~ 7 〇: 9 〇 ~ 3 〇, better β 20 〜 50 : 80 In this case, it is possible to provide a curable resin composition for liquid sealing which is excellent in reliability. Further, in the present invention, the (1) acrylic resin may be combined into a "resin combination" in the combination of 200920091616 27285pif. The resin composition of the epoxy resin is called (3) Thermal radical polymerization initiator The compound of the thermal radical polymerization initiator, that is, the heat-correcting energy, decomposes the radical. Such a thermal radical polymerization initiator ^ is a case where the liquid crystal sealing agent is hardened by the heat of combination of the base species. After the s substrate is added by the better 'thermal radical polymerization gliding in 3 (TC ~ 8 (TC range ^ + day half-life temperature is 5 (TC ~ 70t. Sleeve (7) ^ ^ (four) ~ order ' Especially good base polymerization initiator in the gas _. = degree ^ = half of the temperature when the heat is free. Using KH, the half-life to the original thermal radical polymerization initiator liquid crystal internalization The balance is good. The squeaky and sturdy liquid 曰 ν; the ϊΐ is equal to the excessive decrease in viscosity, which is better to suppress the above viscosity _ resin composition: (4) (four) and accelerate gelation. The gelatinization of the ..., the free-radical polymerization initiator has a 10-hour half-life of 'g8〇 °C, more preferably less than or equal to 耽.': When the upper material is heated and hardened (usually the hardening temperature is 8 〇t~15〇t), it is easy to suppress the heat-hardening ς 25 25 200900816 is too low, the half-life temperature of the aging half-life temperature agent is hot, the polymerization starts, or is applied to the substrate. Step (usually t two into the 仃) + 'liquid day and day sealing agent stability is good. 疋 to the pulse here 10 small 4 half-life temperature More than 8 initiators are difficult to produce free beauty. I, the purpose of the base polymerization of the cheese ..., one, Λ _ from the D sword 10 hours half-life temperature is less than 30 ° C; to the dish can also be hard to react Therefore, the heat-based polymerization initiation _liquid crystal sealing_viscosity stability is remarkably lowered. According to the above, it is preferred that the 10-hour half-life temperature of the thermal radical polymerization initiator is within the above range. _ 10 hour half life The temperature can be specifically determined as follows. First, if the hot knife solution reaction is regarded as a first-order reaction formula, the following relationship holds.

In (C〇/Ct) = kdxt c〇: initial concentration of thermal radical initiator ct: concentration of thermal radical initiator after t hours kd · 'thermal decomposition rate constant t: reaction time 26 200900816 27285pif half-life It means that the concentration of the thermal radical polymerization initiator is reduced to a normal time, that is, the time in the case of Ct=C〇/2. Therefore, after the hour, when the thermal radical polymerization initiator reaches the half life, the following formula holds. Kd = (1/t) χ1η2 On the other hand, since the temperature dependence of the rate constant is expressed by the Arrhenius 1 equation, the following formula holds. Kd = Aexp (-ΔΕ/RT) The following equation can be derived from the above formula. (1/t) xln2 = Aexp (-ΔΕ/RT) A: frequency factor △ E : activation energy R: gas constant (8.314 J/mol. K) τ : absolute temperature (K) The values of A and ΔΕ are revealed in j Polymer by Brandrup et al.

HandBook fourth edition, volume 1, Π ~ Π -69, WILEY-INTERSCIENCE (1999). From the above, if t = 10 hours, the 10-hour half-life temperature τ can be obtained. Well-known compounds can be used as the thermal radical polymerization initiator. Its representative examples include the organic peroxide 'azo compound (aZ〇_C〇mp〇und). 27 200900816 Ζ/Ζ6〇ρΐΤ Organic peroxides are preferably classified as ketone peroxide 'per 〇 ketket, hydroperoxide j hydr〇per〇xide ), dialkyl Peroxide (this 丨 四 四 ) )), peroxyester, diacyl peroxide, peroxidation However, it is not particularly limited, and a well-known organic peroxide can be used. Specific examples of the above organic peroxides are shown below. The number in parentheses refers to the 10-hour half-life temperature (refer to the Wako Pure Chemicals Catalog, Apl).

Corporation catalogue and the above p〇iymer HandB〇〇k). Examples of the oxy ketones produced include methyl ethyl ketone peroxide (1 〇 9r ), hexanone peroxide (1 〇〇 〇), and the like. Further, examples of the peroxy ketals include .1,1-bis(Third hexylperoxy)·3,3,5·trimethylcyclohexane (87〇c), 1,1-double (second Hexyl peroxidation) cyclohexene (87 ° c), 1,; [_ double (t-butyl peroxy) 3⁄4 hexane (91 ° C), 2,2-bis (t-butyl peroxy) butyl Alkane (1〇3 c), ι,ι-(third amyl peroxide) cyclohexane (93ΐ), 4,4_bis(t-butylperoxy)pentanoic acid n-butyl vinegar (105t), 2 , 2_bis(4,4_di-t-butylperoxycyclohexyl)propane (953⁄4 ). . Examples of hydroperoxides include: hydrogen peroxide versus menthane (128 ° C), diisopropyl hydrazine hydroperoxide (145 ° C) (diis〇 propylbenzene hydr〇peroxide), u, 3, 3_4 Butyl butyl hydroperoxide (i53〇c), emulsified hydrogen cumene (156. 〇, 帛 tributyl hydroperoxide (167. 〇, etc.. Examples of di-based peroxide include bis (third butyl) Base oxidized) diisopropylbenzene (1I9 ° C), diisopropylphenyl peroxide (116. d1Cumyl peroxide, 2,5-dimethyl-2,5_bis (t-butyl) Oxidation) 28 200900816 27285 pif Hexane (118C), a second butyl isopropyl carbamide peroxide (12 〇. 〇, a third amyl peroxide U23X:), a di-tert-butyl peroxide (124). 〇), 2,5-monomethyl-2,5-bis(t-butylperoxy)_3_hexene (129 it) Examples of peroxyesters include: cumene peroxy neodecanoate (cumyl per〇Xyne〇deCan〇ate ) ( 37. 〇), peroxy neodecanoic acid, 1,1,3,3-tetramethylbutyl ester (41. 〇, perhexyl peroxy neodecanoate ( 45 C ), peroxy neodecanoic acid second butyl ester (4yc), peroxy neodecanoic acid (Ίpentyl ester (46t:), perhexyl peroxypivalate (53), third butyl peroxypivalate (55 ° C), third amyl peroxypivalate (55). 〇, 'U,3,3-tetramethylbutyl peroxy 2-ethylhexanoate (65£3(:), 2,5_:τ-group-2,5-bis(2-ethylhexyl) Peroxidation) (66. 〇), peroxidation: trihexyl ethylhexanoate (70 C), tert-butyl peroxy 2-ethylhexanoate (72 ° C), 2-B peroxide Third amyl hexanoate (7rc), third butyl peroxybutyrate (82 ° C), hexyl isopropyl monocarbonate (95 〇), maleic acid peroxide Tributyl ester (% ° c), third amyl peroxyoctanoate (96 ( ° C), third amyl peroxyisophthalate (96. 〇, peroxidation 3, 55 曰 trimethyl hexanoic acid Third vinegar (97 C), oxidized lauric acid, third butyl vinegar (98. 匸), pervaporated butyl butyl phthalate (99. 〇, 过 过 厶 美 己 单 单 单 第三Butyl ester (99 ° C), trihexyl peroxydecanoate ^99 it), 2,5-dimethyl-2,5-bis(phenylhydrazine peroxy)hexane (1〇〇^ ), Oxidized acetic acid third amyl ester (100 ° C), benzoic acid benzoic acid third pentane g ° C), peracetic acid tert-butyl acetate (102 ° C), benzoic acid benzoic acid tributyl acrylate (104 〇 C) — Examples of the dimercapto peroxides include: diisobutyl hydrazino peroxide 29 200900816 ), a _3,5,5-trimethylhexyl decyl peroxide (60. 〇), 2 laurel 1 peroxide (10)), oxidized sulphate (_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Di-n-propanedicarbonate dicarbonate: diisopropyl hydrazine dicarbonate (41 ° C), dicarbenium oxyhydroxide = (wood t-butylcyclohexyl) vinegar (4rc), di-dicarbonate di-2 -

^土己_ (44 ° C), peracetic acid propyl carbonate third vinegar (96. 〇, peroxy 2-ethylhexyl carbonate third oxime ester (99. 〇. heart, '", people' right An argon compound (also referred to as an azo-based thermal radical polymerization initiator) which acts as a thermal radical polymerization initiator is described. Examples of the azo-based thermal radical polymerization initiator include: water-soluble oxime Thermal radical polymerization, initiator, oil-soluble azo thermal radical polymerization initiator, polymer azo anthracene thermal radical polymerization initiator. Examples of water-soluble azo thermal radical polymerization initiator Including: 2,2,-azobis(2-imidazolin-2-yl)propane]disulfate dihydrate (46 〇) 2'2·azobis[N-fluorenylcarboxyethyl)- ; 2-mercaptopropyl hydrazine] hydrate (5? ^), 2,2'-azobis(2_[1-(2-transethylethyl)mazoline-2-yl]propane} Acid salt (603⁄4), 2,2|-azobis(1-imino-1-pyrrolidino-2-ylpropane) dihydrochloride (67 ° C), 2,2'-azo double [ 2-methyl_N_(2-hydroxyl)propylamine](87 C ), 2,2-azobis[2-(2-m-mistyl-2-yl)propanone], hydrochloride (44 〇 2,2,_Azobis(2-mercaptopropionamidine) dihydrochloride (56^), 2,2'-azobis[2-(2-imidazolin-2-yl)propyl] 61〇c ), 2, 2, · Even. Nitrogen, {2 methyl Ν-[ι,ι_ bis(light-based methyl)_2_ylidylethyl]propanamide} ( 8〇30 200900816 27285pif Examples of oil-soluble azo-based thermal radical polymerization initiators include: 2,2,-azobis(4-methoxy from dimethylformonitrile) (3叱), 2,2,_even double (2_monodecyl methacrylate) (66 ° c ), hydrazine, Γ-azobis(cyclohexane-1-carbonitrile) (88 C ) 1,1 [(cyano-1-indenyl) Azo]carbamamine (1〇4.〇), 2,2'-azobis(Ν-cyclohexylmethylpropionamide)(iiit), 2,2,_azo double (2 , 4· dimethyl, nitrile) (5rc), 2, 2, azobis(2-methylbutyronitrile) (6rc),

2,2'-azobis[Ν·(2-propenyl)-2-mercaptopropionic acid amine](96.(:), 2,2,-azobis(N-butyl-2-methyl) Propylamine (11 〇). An example of a knife azo-based thermal radical polymerization initiator includes: a polymer azo-based thermal radical polymerization initiator containing polydimethyl carbaryl 2. A polymer green-green radical polymerization initiator containing a red binary material, etc. Further, a mixture of any of these compounds may be used as a thermal radical polymerization initiator. In the resin combination of the above (1) and (2), the radical polymerization initiator is preferably from 001 parts by weight to 30 parts by weight, and the amount of the thermal radical polymerization initiator is too large, and the viscosity stability is deteriorated. When the amount of the polymerization initiator is too small, the hardenability is deteriorated. (4) The filler is a filler which is used to control the viscosity of the liquid crystal sealing agent, the strength of the hardened product, and the control line expansion property.娜expansion) etc. == Filling agent. By filling the filler, the liquid crystal sealant can be improved. If the filler is used in the field of common electronic materials, There are no restrictions on the filling. 〃 钡 钡 钡 钡 钡 钡 钡 钡 钡 钡 钡 钡 钡 钡 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 Aluminum ^alumma), zinc oxide, cerium oxide, potassium titanate, kaoliniin, talc, giass beads, sericite, activated clay, Inorganic filler of bentonite (bentonite) and iuh slave tantalum nitride. Further, an organic filler may be used in the present invention. The term "organic filler" means that the softening point temperature is usually greater than 120 as measured by the ring and ball method (JACT test method: Rs_2). (: an organic compound. Among them, rubber particles having a softening point less than or equal to room temperature in the present month can also be used as an organic filler. Examples of the organic filler include: polydecyl acrylate, polystyrene and a copolymer, a polyester fine particle, a polyurethane fine particle, and a rubber fine particle formed by copolymerization of a monomer copolymerized therewith, wherein the linear expansion ratio of the liquid crystal sealing agent can be kept low. In terms of shape, the filler is preferably an inorganic filler, and it is particularly preferable that the cerium oxide and talc are difficult to permeate due to ultraviolet rays. No matter the inorganic or organic filler, the shape of the filler is not particularly special. That is, a filler of any shape such as a spherical shape, a plate shape, or a needle shape, or a non-fixed shape may be used. Further, the average primary particle diameter of the filler is preferably L5 _ or less, and The specific surface area is preferably from 1 m 2 /g to 500 m 2 /g. The curable resin composition for liquid crystal sealing containing such a filler has good balance between thixotropy and viscosity. Average-secondary particle size of the filler By〗 ISZ8825_1 napkin disclosed laser riding Shen Diffractometry v) is measured, the measurement may be disclosed by Jisz8 ^ BET method (Bmnauer-Emmett-Tdler meth〇d) the specific surface area was measured for 32 200900816 27285pif. Or two or more: ==::: From the point of view, it is better to use two kinds of materials to mean that the material is not used. Two or more kinds of fillers with two or more kinds of filling materials but different average particle diameters, the material phase is two: flat, and the filler is 10 parts by weight to 3 〇 by weight of Si: ~50 In parts by weight, it is easier to use for liquid crystal sealing: the filling amount of tLf4 is controlled in the range of u~5.0 in the above range, and the data of the thixotropic index of the curable resin composition is used. . The above thixotropic index is the viscosity _ value of root 嶋 ==: 2rr5 (four). 5·〇 〇 rpm viscosity; | and obtained (5) epoxy hardener liquid crystal sealing with curable resin composed of oxygen hardening, preferably latent two or two 'agent room to epoxy resin, = deflated Epoxy hard hardener. By the thermosetting property of the product I. W-crystal seals for hardening trees. The latent epoxy hardeners can be used. Among them, in the case of the survey 33 200900816 ζ /ζδ^ρΐΓ excellent stability, it is better that the temperature of the softening point measured by the ring and ball method is greater than or equal to the touch. a latent epoxy hardener for c. Examples of the inclusion of this smear epoxy wei group can be used as a liquid-type epoxy hardener: ······························································ And its derivatives, dicyandiamide, ar〇matic amine, and the like. These latent epoxy hardeners can be suitably combined into a mixture. The screen printing or dispensing crying used in coating the composition is difficult to maintain due to the long residence time of the composition in the apparatus, and the composition is inferior in stability. In this respect, in particular, a composition containing a neodymium or an amine-based latent hardener having a softening point temperature greater than that of the specific one measured by the ring and ball method is extremely excellent in viscosity stability at room temperature. Used for a long time in screen printing or dispensers. . Examples of the above amine-based latent curing agent include dicyandiamides such as dicyandiamide (melting point: 209C); diterpene adipate (melting point: 181. 〇), 1, hydrazine (mercaptocarbonylethyl) -5-isopropylethyl carbazide ((10) carb0ethyl)-5-iS0pr0pyl hydantoin) (refining point is l2 (TC), dodecanedioic acid dihydrazide (melting point 190. bismuth, azelaic acid diterpenoid) (melting point C) _ and other organic acid dioxins; 2,4-diamino _6_[2,_ethylimidazolium oxime,-beauty]ethyltriazine (melting point 215t~225t), 2_benzene An imidazole derivative such as a thiol imidazole (melting point is 137 C to 147 ° C). The weight of the curable resin composition for liquid crystal sealing excellent in viscosity stability and subsequent reliability is relative to 1 〇〇. The content of the resin, and δ, the latent epoxy hardener is preferably 3 parts by weight to 3% by weight. The crystallization method is preferably used by a water washing method or a (6) epoxy resin. The curable resin for resin liquid crystal sealing can also be used as a resin. The epoxy resin of the present invention is a compound of an epoxy group having an oxygen tree or more (in which: Examples of the epoxy tree (4) in the sputum include = ί; and the above aromatic diols are ethylene glycol: propyl alcohols, f, (epi 〇 Worohy, the material of the family is shrinking: reaction double ^ As a raw material, the manufacturer 2 2 will be a varnish resin which is opened by the benzene or the age of the formic acid, and the styrene resin or the copolymer thereof. The polystyyl chlorohydrin obtained by the reaction of ''^^^101)' and 'table' (4) uy] yieneph-resm) is a varnish-type epoxy resin. Epoxy tree gambling, triphenyl sulphate;, Lu Yuexi: double age A type epoxy resin, double age F type wax, three stupid _ epoxy tree: type benzene age Ethylene epoxy resin, joint - It is formed by the epoxy resin and phenyl ether type. The high purity is carried out by the knife retort method. 35 200900816 It is better to be equal to the thief, and the aging point is greater than: if epoxy The softening point of the resin is 〜10_. The reason is that the solubility of the epoxy resin in the liquid crystal = the amount of the knife in the above range, the display characteristics of the crystal display panel, and the diffusibility are low, and the obtained liquid 2, the above (1) propylene Acid resin: on, ring

Rely on sex. From this point of view, the weight average amount of the article having a molecular weight of 1000 to 2000 in the range of 1000 to 2000 can be determined, for example, by (7) photoradical polymerization initiation. The liquid crystal sealing is composed of a curable resin. The substance may also contain a t-initiator. The household is said to be light free. The human body produces white * its secret person ^ base agent, which refers to a compound which can be free radical by light. The liquid crystal dense composition of the initiator can be temporarily cured by photohardening. Therefore, the curable resin composition for liquid crystal sealing I may not be a photoradical polymerization initiator. The hardened hybrid test for the liquid positive seal of the polymerization initiator can be hardened only by heating (four), so that it can be omitted from the cost; § · The advantage of the photohardening step of the surface is large. Photoradical polymerization initiator It is not particularly limited, and well-known compounds can be used, for example, including: benzoin-based compounds, acetophenones, benzophenones, thiophenanthones, and α-mercaptopurines. g purpose _acyl〇xime ester), phenyl glyoxylate, benzyl 36 200900816 27285pif, oxime compound, diphenylsulfide compound, acyl phosphine oxide ) compounds, organic dye compounds, iron phthalocyanine, benzoin, benzoin ether, anthraquinone

The content of the photoradical polymerization initiator is preferably 0.1 part by weight to 5% by weight based on 100 parts by weight of the resin combination, more preferably 0.3 part by weight to 5.0 parts by weight. The photoradical polymerization initiator is more than 0.3 parts by weight of the composition, and the hardenability by light irradiation is good. On the other hand, the composition of the photoradical polymerization initiator having a content of 5 Å or less by weight or less is excellent in stability when applied to a substrate. When the resin composition containing a photoradical polymerization initiator is hardened, the light source is preferably ultraviolet light, visible light or the like. Further, the amount of light irradiation is preferably 500 mJ/cm2 to 1800 mj/em2. (8) Thermoplastic polymer

The curable resin composition for liquid crystal sealing may further contain a thermoplastic polymer. The known thermally heteropolymer is formed by molding a polymer compound having a target shape. ^趴 thus J is 50^2^7 towel (four) plastic wire compound hybrid point temperature is usually 50C~120C, preferably is the same as the above-mentioned van _, then in the above resin (four) reading point, the dish in the character will In the group of two cores: when the heat is hardened, the thermoplastic polymer is polymerized for one month, (2) the shell is modified by the resin, and (6) the ring is heated. The composition is reduced by _degree, and the phase and the three phase valleys are Inhibition of beer is low, which can suppress liquid crystal line leakage and the like. 37 200900816 The content of the thermoplastic polymer is preferably 1 part by weight to 3 parts by weight based on 100 parts by weight of the resin combination. The above softening point temperature can be measured by a ball method (JACT test method: rs-2). Further, since the thermoplastic polymer exhibits good compatibility in the curable resin group for a liquid crystal sealing agent, it is preferred that the average particle diameter is usually 0.05 (four) to 5 (four), preferably 〇〇7 rotation. ~3 _ range. Such a thermoplastic polymer can be used as is well known, preferably 50 Wt% to 99.9 wt% (by weight): 5 wt% to 〇% of the station (more preferably 60 wt% to 80 wt%: 4) 〇wt%~2〇研%), a copolymer obtained by copolymerizing a (meth)acrylic acid S monomer and a silk-blendable body with the monomer. Further, the above-mentioned total (four) is preferably a copolymer formed by polymerization in an emulsion state, such as emulsion p〇 lymerization or suspension polymerization (clear polymerization). Examples of the above-mentioned (meth)acrylic acid-based monomer include (meth)acrylic acid methyl vinegar, (meth)acrylic acid ethyl vinegar, (meth)acrylic acid vinegar, acrylic acid butyl vinegar, (methyl) 2-ethylhexyl acrylate, (meth)acrylic acid, 16 s, (meth)acrylic acid octadecyl, (meth)acrylic acid butyl I), ethyl (meth) acrylate phenoxy Vinegar, (meth) (10) acid 2 - a monofunctional (meth) propyl monomer such as acetaminophen, glycidyl (meth) acrylate or a mixture of such monomers. The towel is preferably a mixture of (meth)(10) acid methyl vinegar, acryl butyl acrylate or (mercapto)acrylic acid 2 ethyl group or a monomer thereof. Examples of the monomer which can be combined with the above (¥基)_咖赖it include: acrylamide; (meth)acrylic acid, itacon 38 200900816 27285pif acid (itaconic acid), horse Acid monomer such as maleic acid; aromatic vinyl compound such as styrene or styrene derivative; 1,3-butadiene, 1,3-pentadiene, isoprene, 1,3· A conjugated diene such as dichloro, chloroprene or a polyfunctional monomer such as divinylbenzene or diacrylate. These monomers can also be used in combination. (9) Other additives The curable resin composition for liquid crystal sealing I may further contain a coupling agent such as a silane coupling agent, an ion trapping agent, or an ion exchanger. Agent), a homogenizing agent, a pigment, a dye, a plasticizing agent, an antifoaming agent, and the like. Further, in order to adjust the gap of the liquid crystal display panel, a spacer or the like may be disposed. The second liquid crystal sealing curable resin composition of the present invention is characterized in that it contains (10) 1 molecule in addition to the above (3) thermal radical polymerization initiator and (4) filler. A radically curable resin of a radically polymerized carbon-carbon double bond and a (U) radical chain transfer agent. The curable resin composition for liquid crystal sealing of the present invention having the above-described characteristics is also referred to as "curable resin composition for liquid crystal sealing" or "resin composition". Specific examples of the (3) thermal radical polymerization initiator and (4) filler contained in the resin composition crucible are as described above. Among them, the (3) thermal radical polymerization initiator of the resin composition is particularly preferably an organic peroxide, an azo compound, a benzoin, a benzoin ether or an acetophenone. 39 200900816 (10) A radically curable resin having a carbon-carbon double bond capable of undergoing radical polymerization in one molecule, and a radical curable property of a carbon-carbon double bond capable of undergoing radical polymerization in one molecule of the present invention The resin (also simply referred to as "radical curable resin") refers to a compound having a carbon-carbon double bond capable of undergoing radical polymerization such as an ethylenically unsaturated bond in one molecule.

Examples of the radical curable resin include a (meth) acrylate monomer or a like polymer, an allyl alcohol derivative, and a vinyl compound, and are not particularly limited. The above (1) acrylic resin and (2) modified epoxy resin are included in the above-mentioned radical curable resin. The oligomer of the above (meth) acrylate monomer or the like is not particularly limited, and includes, for example, those exemplified above. ^Examples of the above allyl alcohol derivatives include: triallyl cyanurate, iso-, urinary mono-ene, maleic acid di-propyl propylene glycol, adipic acid diene vinegar, ortho-J dicarboxylic acid diene propylene Ester, diallyl isophthalate, trimellitic acid tris, propionate, tetraallyl pyromellitate, dipotassium glycerin, trimethyl propyl propylene pentaerythritol diene Pentaerythritol, tri-propyl propyl scales, and propylene-dyed days. Examples of the above vinyl compound include diethylbenzene benzene. I contains ίί free radical curable resin, which can be used in one molecule. The carbon having a different functional group such as a functional group and an epoxy group is preferably a (meth) acrylonitrile group; a different functional group epoxy group and a 2-radical curable resin. The (meth) acrylonitrile group in the frame is combined with other radical sclerosis tree 40 200900816 27285pif = = = = = = = = = = = Freedom, hardenability, and more, the reliability is also good.

Fed〇rs ^ (1) Sexuality, the second ship 1 dissolves in the liquid crystal in this free radical curable resin. (14) The liquid crystal display of the composition containing the radical curable resin In addition, since the free radical = the tree and the (6) epoxy resin have good compatibility, the product can be homogenized, so that the molecular weight and solubility parameters of the resin group excellent in reliability can be provided (4) The calculation method of the value is the same as the method suggested in the description of the enoic acid resin, so the (η) radical chain transfer agent is freely represented by the chain transfer agent (7) such as Ti4^ in the radical polymerization reaction. Sex transfer compound. Free radical radical) (P ·) 庳: () does not 'with increasing free radicals (ProP Qing ting (T.). The so-called growth ^ generates a radical initiator with new polymerization activation energy ^ (Ρ. In the meantime, the polymerizable compound is sequentially added to the new radical formed by the addition of the two groups. The compound (M) and f (T.) are as shown in the following formula (2). And the accumulation of free radicals (Ρ1.). 41 200900816 The force of the evil spirits (3) shows that the growth-freeness rate constant generated by the Liguline compound is set to Κρ, and the following formula (1) The positive and negative library 2 = positive growth rate in order to generate a free radical chain transfer reaction, it must be set to ktr, the details of the radical reaction shown here are disclosed in the outside, the first part of the Polymerization HandBook (year) Lcal (1)Ρ.+Τ_ρ + Τ. Μ寺肀. Equation (2) Τ. +Μ—Ρ1 ·

(3) Ρ* + Μ·-Ρ2. The sclerosing resin composition for liquid crystal sealing of the present invention having a radical chain transfer agent as described above, which is a growth radical which is formed during the hardening reaction. The reaction of the above formula () is more likely to occur than the above formula (3). That is, it is easy to generate a radical Τ·. Τ. According to formula (2), it reacts with a polymerizable compound to form hydrazine 1. Ρ1. Further, a new ruthenium radical is produced according to the reaction of the formula (1). Since the reaction of the above formulas (1) and (2) is carried out continuously, a large amount of radicals such as τ., ρι, etc. are generated in the liquid crystal sealing agent. Therefore, the radicals can reach the entire surface of the liquid crystal sealing agent. The hardening reaction is carried out efficiently. As a result, the rate of consumption of the polymerizable compound is increased, the curing time of the liquid crystal sealing agent is shortened, and the amount of the uncured polymerizable compound contained in the liquid crystal sealing agent after curing is reduced. Examples of the above radical chain transfer agent include: i) mercaptans, i〇α-methylstyrene dimers, iii) terminally unsaturated mercaptoacrylates, iv) diphenyl disulfide, etc. Thioethers, and v) porphyrin-cobalt complex type sheets. 42 200900816 27285pif i) Mercaptans ▲ Among them, free radical chain transfer thiols for the following reasons. The term "mercaptan" means that in the molecule of j, ^ :=: =, and thus the addition reactivity of the other carbon-carbon double bond of the radical curing resin is exhibited. Therefore, if a thiol is used as a radical chain transfer agent,

In addition to the above-mentioned radical chain transfer reaction, the above-mentioned addition reaction can be caused, so that the curing rate of the liquid crystal sealing agent can be increased. Further, the thiol group also exhibits addition reactivity to the epoxy group. Therefore, the resin composition of the present invention is as follows. [In addition to the above-mentioned components, the resin composition containing an epoxy group-containing compound as in the above (6) epoxy resin may further increase the curing rate. Further, the hardening reaction accompanying the radical chain transfer reaction generally increases the curing rate, but lowers the molecular weight of the cured product. However, when a mercaptan is used as the radical chain transfer agent, the molecular growth effect of the cured product by the above-described addition reaction can be expected, and further, it is possible to further improve the strength of the liquid crystal sealing agent after curing. Effect. Examples of the mercaptans which can be used as the radical chain transfer agent include: (i-1) mercaptoester, (i-2) aliphatic polythiol, (i-3) aromatic Group of polythiols, (i-4) thiol modified reactive silicon oil (silicon oil). The (i-1) thiol ester refers to an ester thiol compound obtained by reacting a mercaptocarboxylic acid with a polyhydric alcohol. Hereinafter, the mercaptocarboxylic acid, the polyhydric alcohol, and the mercaptoester which can be used to obtain the Weiji vinegar will be described. 43 200900816 / ^υ_/ριι Examples of the above-mentioned Weiji retinoic acid include: thioglycolic acid, 2·weikipropionic acid, 3-weisylpropionic acid, 2-sulfisoisobutyric acid, 3-weiki Isobutyric acid. Examples of the above polyol include: ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trishydroxypropylpropane, bis(trihydroxymethylpropane), pentaerythritol, dipentaerythritol , I, 3, 5-tris(2-p-ethylethyl)isotricyanoic acid, sorbitol. Examples of the above mercapto esters include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-propionylpropionate), and 2-cisylpropionic acid 2-ethylhexyl ester. (i-2) Examples of the aliphatic polythiol include: decyl mercaptan, ethanedithiol, propylene dithiol, 1,6-hexanedithiol, 1,1 fluorene-dithiol, diethyl Diglycol dimercaptan, triethylenedithiol, tetraethylenedithiol, thio-ethanedithiol, thiotriethyldithiol, thiotetraethylenedithiol. Further, a cyclic thioether compound such as a polythiol compound containing a 1,4-dithiane ring or an addition reaction of an episulfide sulphur (episulflderesin) with an active hydride such as an amine The obtained cyclosulfide-modified polythiol or the like is also included in the above aliphatic polythiol. (i-3) Examples of the aromatic polythiol include toluene-2,4-dithiol and xylenedithiol. Further, ((4) Examples of the thiol-modified reactive lycopene oil include a 1-based modified dimethyl-Wei-sinter, a M-based modified bis-diphenyl oxaxan. The above-mentioned thiols include a -stage thiol, and Class thiols. The term "first-order thiols" refers to a thiol compound in which a hydrocarbon group is bonded to a carbon bonded to a thiol group. The so-called secondary thiol refers to a bond with a thiol group. Bonded carbon upper bond 44 200900816 27285pif has two hydrocarbyl thiol compounds. Right-use mercaptan as a radical chain transfer agent, as described above, its addition reactivity with carbon-carbon double bond groups It is excellent in the physical properties of the cured product, and therefore, the reactivity is high, and the storage stability of the liquid crystal sealing agent may be lowered. On the other hand, the addition of the secondary thiol and the carbon-carbon double bond group is added. The reaction is inferior to the grade thiol, and therefore has an advantage of excellent storage stability of the liquid crystal sealing agent. Therefore, the radical chain transfer of the present invention ('> ship is a secondary thiol. Containing such secondary sulfur The liquid crystal sealing agent for alcohol is particularly suitable for a so-called liquid crystal sealing agent as described below. The secondary thiol is preferably one having two or more secondary thiol groups in the molecule and having a number average molecular weight of 4 Å to 2 Å. The liquid crystal sealing agent containing the radical chain transfer agent is used. When the agent is hardened, if the radical chain transfer agent does not enter the crosslinked body and remains as a monomer, the radical chain transfer agent dissolves and diffuses in the liquid crystal, and the manufactured product is reduced. The display characteristics of the liquid crystal display panel. On the other hand, the polyfunctional secondary thiol having a number average molecular weight of 400 to 2000 easily enters the crosslinked body. Therefore, the liquid crystal sealing agent containing the radical chain transfer agent is not easy. Since the liquid crystal display panel is dissolved and diffused, the display characteristics of the liquid crystal display panel produced are good. The secondary thiol as described above is preferably obtained by reacting a polyol with a secondary mercaptocarboxylic acid as described above. Examples of the secondary thiol having a number average molecular weight of from 4 〇〇 to 2,000 include: the above pentaerythritol tetradecanoic acid vinegar (the number average molecular weight is 544 8), and the tris(3)-tert-butoxyethyl)-1 ,3,5-triazine -2,4,6 (111, 3 511)-trione) (the number average molecular weight is 45 200900816 / ^u^/yn 567·7). The number average molecular weight of the radical chain transfer agent can be measured, for example, by GPC, using polystyrene as a standard.曰 Its-human's description of chain transfer agents other than thiols. Ii) α-methylstyrene dimers. The α-mercaptostyrene dimer is a compound having a function of a %-carbon double bond in the molecule and functioning as an addition-fragmentation chain transfer agent. Examples of the above-mentioned mercaptostyrene dimers include: 2,4-dipyridylmethylpentene, 2,4-diphenylmethyl-2-pentene, and triterpene Printed (H^trimethyl-S-phenyl indane). The methylstyrene dimer of the present invention is not particularly limited, and those known to the public can be used. Iii) Terminal unsaturated methacrylic acid _ class The term terminal unsaturated methacrylate is a methacrylate compound having an unsaturated bond at the end and contributing to an addition reaction. Examples of such terminally unsaturated methyl propyl phthalates include: monomers, dimers, η polymers. Iv) Disulfide Examples of dioxins include diphenyl sulfide, polythioether modified epoxy resin, and diethoxydecane-polysulfide polymer. v) Examples of porphyrin cobalt complex porphyrin cobalt complexes include: tetra(2,4,6-trimethylphenyl) porphyrin (cobalt (n) tetramesitylporphyrin) complex, four Cobalt (HI) tetraphenyl porphyrin complex. Another 46 200900816 27285pif, the cobalt complex may also be c〇-ch2c(ch3)3, c〇_ch(co2ch3)ch3, c〇-ch(co2ch3)ch2ch(co2ch3)ch3. The free radical chain transfer agent can also be one having an initial transfer interminator. The term "terminating transfer termination" refers to the property of three functions of a radical polymerization initiator, a radical chain transfer agent, and a radical terminator. Such a radical chain transfer agent having an initial transfer termination property can generate a reverse reaction of the above formula (丨) by providing light energy or thermal energy, thereby allowing radicals to undergo chain transfer and improving the hardenability of the liquid crystal sealing agent. . Examples of the above radical chain transfer agent having an initial transfer terminator include a thiocarbamate compound such as tetraethylthiuram disulfide, and a triphenylsulfonium azo group. Benzene, tetraphenyl ethene derivative. The curable resin composition for liquid crystal sealing may further contain the above (5) epoxy curing agent and (6) epoxy in addition to the above (3), (4), (1), and (11). Resin, (7) photoradical polymerization initiator, (8) thermoplastic, polymer, (9) other additives. The details of the above-mentioned compounds and the like, and the Tanedo Valley have been described above, and thus the description thereof will be omitted. >士;树月曰,和成物;[[中, The amount of each component is not particularly limited, in terms of the hardening property or storage stability of the lipid composition ,, it is better The content of the (1)-radical polymerization initiator in the above (1Q) radical curable resin of 1 GG parts by weight is 4 0.01 parts by weight to 5.5% by weight. The residual material of the tree is excellent in the curability of the thermal radicals, and the cured product and the adhesion strength of the substrate are improved. In the case where the content of the (10) radical resin <(3) thermal radical polymerization initiator is more than 5 parts by weight, the viscosity stability of the resin composition 变 is deteriorated. On the other hand, when the content is less than 0.01 part by weight, the amount of the thermal radical polymerization initiator is too small, and the curability of the resin composition JI may be lowered. Further, with respect to the (10) radical curable resin, the (11) radical chain and the content of the shifting agent are preferably _ parts by weight to 5 parts. Parts by weight, more ς 2, are 0.05 parts by weight to 3.0 parts by weight. The resin composition has a stable viscosity and excellent properties. Even when the wiring on the substrate is reddish and fine, the curing reaction of the composition π can be sufficiently performed, so that it is not cured = two, thereby suppressing the liquid crystal (tetra) liquid crystal. Pollution. Among them, in the case of a phase-radical-curable resin, (11) the above-mentioned hydrazine is produced, and the hardening reaction such as the production of (10) radical-curable resin ί is excessively performed, and the softening reaction is not properly performed. Sometimes it gets worse. On the other hand, if (1) the content is less than GQ1 conversion ff, and the resin composition she = part ~ 25 Ha 3G weighs 1 part, it is better that the 5 weight is high and the flow "sometimes it will decrease. Another aspect: The hardening strength of the formed hardened material is lowered. As far as the right, the, and the machine filler are small, the moisture resistance is sometimes adjusted, and the content of the inorganic filler is adjusted to the upper 48 200900816 27285pif The adhesive strength of the cured product and the substrate may be characteristic of each radical hardening tree such as hardenability or storage stability; and it is more preferably 2 weights relative to the weight of the (10) 削) part by weight ^^ = " is 1 part by weight ~: The resin composition D in the exhaustion can maintain excellent concentricity and can be made into a highly reliable liquid crystal display surface; Further, in the composition of the eucalyptus wax, the tongue f曰U is not a double-walled curable resin, and (4) the epoxy tree is replaced by (10) free 40 parts by weight. The reading of the bribe is 1 part by weight ~ the resin composition Ε fabric is the amount of the resin composition π viscosity can be adjusted according to the composition of each component = i section. Use a Ε-type viscometer to coat the resin with H5-degree (initial viscosity) within the above range due to uneven coating of == ί. Where 'if the initial viscosity is 5 〇 or more, the seal after coating The retention is especially excellent. The so-called seal shape retention property is a property that the seal shape remains unchanged after a period of time.曰: Degree is greater than # 15〇 Pa_s ’ and the seal shape retention will become / more good. In addition, if the initial viscosity is less than or equal to the weight of the partner, the left side of the knife is sealed by a crystal, and even if the nozzle of the dispensing is a small diameter of O b 49 200900816 mm to 0.5 mm, the coating workability is also good. Further, the thixotropic index of the resin composition Π, i.e., the viscosity at 25 ° C and 0.5 rpm measured at e.g. 〇, 5 〇 print work viscosity 7? 2 ratio 7? 1/7? 2 is better 1.1 to 5.0, more preferably 1.2 to 2.5. The viscosity of the resin composition 是 is obtained by using an E-type rotary adhesive production (for example, a digital rheometer manufactured by BROOKFIELD Co., Ltd., model: DV-guar ULTRA), and has a radius of 12 mm and an angle of 3. Cp_52

The cone-and-plate type sensor was used to place the liquid crystal sealant at a predetermined temperature for a value measured after 5 minutes. The above thixotropic index is as described above, which is the ratio of the viscosity at a lower shear rate to the viscosity measured at a higher shear rate. Therefore, the thixotropy is high, and the high number of fluids are at a low shear rate. It will flow at a high viscosity and will flow at a low viscosity at high shear rates. Therefore, when the above resin composition is applied at a high cutting speed, the above resin composition

Si: Therefore, (4) the coating property of the substrate is good. In the sealing portion formed of the resin composition, the liquid (4) leakage is less likely to occur, and the stalk composition is excellent in the defoaming property of the stalk composition, and the reliability of the sheet is excellent. u to the liquid - no difference: three liquid crystal sealing with a curable resin composition characterized by charging ", more (3) thermal radical polymerization initiator and (4) filling, hydrogen bonding official 1 i ) having a carbon-carbon double bond capable of undergoing radical polymerization, comprising two or two groups selected from the group consisting of = oxy group and the remainder; The amount of hydrogen bond functional group in the resin composition of (12) is 50 200900816 27285pif l_(b^4 m〇i/g~6 0χ10-3 m〇1/g; in the above (12) resin composition The amount of the epoxy group is 1.OxlO4 mol/g to 2.6 x KT3 mol/g. The curable resin composition for liquid crystal sealing of the present invention having the above characteristics is also referred to as "curable resin composition for liquid crystal sealing" or "Resin composition". (12) Resin composition having a carbon-carbon double bond, a hydrogen bond functional group, and an epoxy group capable of undergoing radical polymerization. The curable resin composition for liquid crystal sealing of the present invention comprises Two or more resins from a specific resin group, and having a carbon-carbon double bond capable of undergoing radical polymerization, a hydrogen bond functional group And a resin composition of an epoxy group (also referred to simply as "curable resin"). The carbon-carbon double bond which can be radically polymerized means a functional group which can be polymerized by a radical. Preferable examples of the radically polymerized carbon-carbon double bond include a vinyl group, a propyl group, an acrylonitrile group, and a methyl propyl group. Among them, a carbon-bonded double bond which can be subjected to radical polymerization is preferred. Is a (meth) acrylonitrile group. The hydrogen bond functional group is a functional group or a ligand i (ligand) having a hydrogen bond. Examples of the functional group having a hydrazone bond include: a group, a group, -NHR group (R represents an aliphatic hydrocarbon group, an aromatic group), a _c〇nh2 group, or a group. Examples of the ligand having a hydrogen bond include: -NHCO-coordination group, _CONHC〇-coordination group, Or a hydrazone ligand. In the above, the hydrogen bond functional group of the present invention is preferably a thiol ligand represented by _〇H and an urethane ligand represented by -NHC Ο (Also abbreviated as "amino acetate"). The above (12) curable resin has a (meth) acrylonitrile group.

200900816 ^ ' ·ώ〇^υΐ I 碳 Free radical polymerization of carbon-carbon double bonds. Therefore, the (12) curable resin is included in the above (10) radical curable resin. As described above, the liquid crystal sealing agent is required to have excellent leak resistance. Since the liquid crystal leakage is likely to occur when the liquid crystal sealing agent hardens slowly, when the light is hardened, if the light shielding portion is present, the liquid (four) leakage becomes more. Therefore, the liquid crystal sealing agent is preferably only Hardened by heat. However, in general, when the heat is cured, the viscosity of the liquid crystal sealing agent is lowered, so that liquid crystal leakage occurs even if it is hardened by heating. Therefore, it is effective to reduce the viscosity reduction of the liquid crystal sealing agent upon heating. In order to reduce the viscosity of the liquid crystal sealing agent during heating, it is preferred to increase the hardenability of the curable resin contained in the liquid crystal sealing agent. According to the above, since the amount of the hydrogen bond functional group of the resin in the resin composition m is W-V〇1/g to 6.0xl0-3m〇1/g, the hardening speed is fast. Although the mechanism is not clear, it can be presumed that if a certain amount of hydrogen bond functional group is present, the hardened tree ages will be attracted to each other due to the mutual attraction of hydrogen bonds, thus making the hardening reaction better. Easy to carry out. The age of the resin is rapidly reacted between the carbon-carbon double bonds which are adjacent to each other and the epoxy groups which are close to each other, and the hardening resin of the present invention has a high curing rate. The amount of the gas bond functional group is obtained by dividing the number of the above hydrogen bond functional groups by the radical reaction = resin (5) and the unit is _ / g. When the amount of the hydrogen bond functional group in the curable resin is more than the above upper limit, the water resistance of the liquid crystal sealing agent containing the curable resin may be lowered. On the other hand, if the hydrogen bond functional group 4 in the sclerosing tree is less than the above lower limit, 贞彳 contains the sclerosing property 52 200900816 27285pif, and the hardness of the liquid crystal sealing agent is lowered. According to the above, a liquid crystal gun sealant containing hydrogen and a dienergy base amount of 树脂.〇) <1〇-4 m〇1/g~6 〇xl〇-3 m〇i/g, water resistance Excellent balance with hardenability. Hydrogen bond functional groups are also associated with liquid crystal contamination. Since the liquid crystal is usually hydrophobic, it is not easily compatible (compatible with the compound having a polar group). According to the above, when the amount of the hydrogen bond functional group in the compound is increased, the polarity of the above compound is increased, so that it is difficult to be compatible with the liquid crystal. Therefore, the liquid crystal sealing agent containing a hardening resin in an amount of 1 to 〇xl 〇 -4 mol / g to 6.0 X HT 3 mol / g containing a hydrogen bond functional group is less likely to contaminate the liquid crystal. As described above, the curable resin of the present invention has an epoxy group in the molecule. The % oxy group means a group represented by the following structural formula. The amount of the epoxy group in the curable resin of the present invention is 1〇xl〇_4 m〇i/g 2^6x12 m〇i/g. The amount of the epoxy group is the number of epoxy groups divided by the curable resin. = = and find 'the unit is mQl / g. Since the epoxy group has a high addition polymerization, the curable resin having an epoxy group has high hardenability. Further, the epoxy group can improve the adhesion of the liquid crystal (four) touch glass substrate. The curable resin of the present invention can be obtained by blending _ or two or more kinds of resins selected from the group consisting of the following. (1A) A radical reactive property, which has a hydrogen bond functional group in a molecule and two carbon double bonds capable of radical polymerization, and the hydrogen bond has a basis amount of 1. 5 χ 1 〇 3 m. 〇1/g~6.〇xl(r3 m〇1/g. 53 200900816

200900816 IB ^ A radically reactive resin having a gas bond functional group 丄 epoxy group in the molecule and a carbon-carbon double bond capable of undergoing radical polymerization, and the above hydrogen bond Lu Yue b base is 1.0 x 10 4 mol / g~5.0xl0-3 m〇l/g. / Uc) an epoxy resin having an epoxy group in the molecule but having no carbon-carbon double bond capable of undergoing radical polymerization, and having a softening point of 40 or more as measured by the ring and ball method, and having a weight average The molecular weight is 500~5〇〇〇. The curable resin of the present invention can be prepared by appropriately selecting a resin of (1A) to blush, (4) a hydrogen bond functional group, and an epoxy group in the above-mentioned generalized tree; (1Α) to (1C). The hardening of the present invention! The amount of the hydrazone functional group of the raw tree can be determined in the following manner. The hydrogen bond functional group of C1A) is set; the molecular weight is Ma (g/mol), the compounding ratio is a (wt%) ', ((8) hydrogen bond functional group (tetra) 虮 (one), molecule (g/mol), The blending ratio is b (wt%). The hydrogen bond functional group of the gate (1C) is n 八 (g/mol), and the blending ratio is (t%). The amount of Me energy in the knives can be based on the following formula H. Hydrogen bond functional group amount of hydrogen bond-curable resin > (Na) / (Ma) xa/i〇〇+ (_ , "... /(Mc)xc/100 ^(Mb)xb/100+( Nc) The amount of oxygen can also be obtained in the same way. S;: A) ~ (1C) tree intestines are explained. (1A) Resin is a molecular (4) energy base, and can be freely 54 200900816 27285pif base polymerization A resin having a carbon-carbon double bond and a hydrogen bond functional group of 15% 3_% 6, 0: 1. mc) i / g. In the present invention, 'radical polymerization can be referred to as "double bond", and (5) resin is also W N冉: ', and earth-g-type resin. The radical difunctional resin preferably contains no epoxy group.

The hydrogen bond functional group of the radical difunctional resin can be obtained in the above manner. The value is 1.5 x l 〇 -3 m 〇 l / g 〜 6 0 x l 0 -3 m 〇 1 / g, preferably 1 5 χ 1 (Τ 3 mol / g ~ 3 · 4 χ 10 - 3 m 〇 l / g. Hydrogen bond function The molecular weight of the radical monofunctional resin used in the calculation of the basis amount is preferably determined by GPC and converted to polystyrene. In this case, the number average molecular weight and the weight average molecular weight can be calculated. The amount of the hydrogen bond functional group is preferably calculated based on the number average molecular weight. The radical monofunctional resin can be, for example, a "compound having a double bond and a carboxylic acid in a molecule" and a "compound having a double bond and a hydroxyl group in the molecule". The esterification reaction is carried out. Examples of the "compound having a double bond and a carboxylic acid in the molecule" include (fluorenyl)acrylic acid or a (meth)acrylic acid derivative obtained by reacting (mercapto)acrylic acid with an acid anhydride. Further, the "compound having a double bond and a carboxylic acid in the molecule" may be a compound obtained by adding a 6-hexanolide to an acrylic acid via a base vinegar, and further with an acid needle. A compound obtained by the reaction. Examples of the hydroxyalkyl acrylate include: Hydroxyethyl enoate, hydroxybutyl acrylate. Examples of "compounds having a double bond and a hydroxyl group in the molecule" include: acrylic acid by calcination, 4-pentaerythritol tris(meth)acrylic acid vinegar, sorbitol alcohol 55 200900816

/ ^.O^fUU 'A (曱基) propyl male vinegar. The radical difunctional resin may also undergo a ring-opening addition reaction between an epoxy group of a "compound having a compound in a molecule" and an epoxy group of a "polycondensate of an aromatic diol" (ring-opening addition) Obtained by reaction). Examples of the polyglycidyl sulphate compound of the sulphuric alcohol include bisphenol A, bisphenol S, bisphenol F, bisphenol AD, stear ether, resorcin, and the like. Among them, the free radical difunctional resin is preferably obtained by reacting polyglycidyl = hydrazine (meth) acrylic acid to obtain _ lipid, more preferably; L1 ^ ^ ((4) , or a mixture of these.

In the general formula (al ), ... ϊ R2 R3, H4 are independent —

Rm each independently represents a hydrogen atom or a methyl 'propyl group, a carbon number of 1 to 4 I, an alkyl group having a number of 1 to 4, and an ene group representing an integer of 1 to 4 to a terroir or carbon. The number is 1 to 4 alkoxy groups, and 1 represents an integer of 1 to 4,

The organic group represented by ScV or -〇- is --CH2-, _C(CH3):

200900816 27285pif

General formula (a2), ♦·... General formula (a2) 5 K, & and ruler 8 are respectively independent and distinctly represent atomic or propyl group, and the number of discs is 丨~4 ', each number The alkyl group of 4, the olefinic table -/\ has a superficial basis or the number of breaks is 1 4 Γ 不 〜 〜4##·············· 4 integer

In the general formula (a3), the rule 2, the Rm, the η, the formula (a3) A are the same as those of the formula (a).

Il 4-' r λ\ ...... The general formula (a4) is the same. In the formula (), R5, R6 and the content defined in the formula (5), in the above-mentioned tree wax, 'the radical difunctional resin of the invention is particularly good 57 200900816 is a resin represented by the formula (a3) or (a4) . (1B) Resin (the resin is a resin having a hydrogen bond functional group, an epoxy group, and a double 1 in the molecule, and the amount of the hydrogen bond functional group is 1.0 to 1.0 mol/g to 5.0 ΧΚΓ 3 m〇l/g. (1B) The resin can be obtained by reacting an epoxy group of an epoxy resin with a carboxyl group of (mercapto)acrylic acid or a complex derivative.

The amount of the hydrogen bond functional group of the (1B) resin can be determined in the above manner. The value of the amount of the gas bond functional group is preferably l.〇xl (T4m〇l/g~5.0X10-3 m〇l/g^ = is 1.0xl0'4m〇1/g~3 4xl (r3m〇) 1/g. When calculating the amount of the hydrogen bond functional group, (4) the molecular weight is preferably a number average molecular weight determined by GPC in the same manner as the radical difunctional resin. (1B) Epoxy group of the resin The amount is not particularly limited, and it is preferably 10 mol/g to 6.0 x 10-3 m〇1/g '. More preferably ι 〇χΐ〇_4_

The number average molecular weight of 1 (T3 mol/g. S UB) resin is preferably 岐·~ plus (8). If the number average molecular weight is in this range, the hardening of the lyophilized liquid in the liquid crystal will be lowered. Therefore, the liquid containing this resin is less likely to contaminate the liquid crystal. + Examples of epoxy trees that become the raw material of (1Β) tree wax include

Phenol f clear, epoxy resin, phenol novolak type epoxy resin, bisphenol A type consumption _, (four) F type epoxy resin, three-turn W-type epoxy tree, benzene, benzene, epoxy resin, triphenyl _Epoxy touch, type II epoxy turn, biphenyl type epoxy is difficult. These trees are well-picked by high-purification by means of a molecular distillation method, a washing method, and the like.曰 58 200900816 27285pif An example compound comprising a derivative of (meth)acrylic acid. Specific examples of such a group of If and a compound of (meth) propyl fluorenyl group H include the following reactants: 彳 θ / _, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Dicarboxylic anhydride, trimellitic anhydride, tetracarboxylic anhydride, succinic anhydride, maleic acid, acid, adipic anhydride, turmeric, 丄 ricric read 4 (methyl) propyl oxyethyl benzene Three wild acid wild.

Specific examples of the base group (meth) propylene include: (meth)acrylic acid butyl (meth) propane acid by the propyl group, (meth)acrylic acid 4 _ oxy oxadienoic acid The epoxy oxime adduct, the cyclomethicone of (meth)acrylic acid, and the caprolactone modification of (mercapto)acrylic acid. Since (1B) resin has both an epoxy group and a double bond in the molecule, the compatibility of the bis-functional resin and the (lc) epoxy resin is excellent, and therefore, (m) resin, and ( 1A) Free radical difunctional = di- or dc) The liquid crystal sealing agent of the epoxy resin can provide a uniform cured product: the glass transition temperature (Tg) of the liquid crystal sealing agent is increased, and the strength is increased. (1C) resin

The Uc) resin is a resin having no ethylenically unsaturated double bond in the molecule and having = or more than one epoxy group. The epoxy resin of the present invention has a softening point of 401 or more by a ball method and a weight average of 500 to 5 Å. (1 c) The softening point and molecular weight of the resin may affect the viscosity when the liquid crystal sealing agent is formed. The liquid crystal sealing agent containing the (ic) resin having a softening point and a weight average molecular weight within the above range, in particular, the liquid crystal of the unhardened liquid crystal 59 20090081 & the viscosity of the hardening resin in the sealant is not too low and is in an appropriate range Therefore, the seal pattern is less likely to be deformed and is excellent in leakage resistance. The softening point is not particularly limited as long as it is 40 ° C or more, but the softening point is preferably less than 160 ° C in order to make the viscosity when the liquid crystal sealing agent is formed in an appropriate range. In addition, the liquid crystal sealing agent containing the (ic) resin having a softening point and a weight average molecular weight within the above range is less likely to contaminate the liquid crystal because the solubility (1C) of the resin in the liquid crystal is lowered and the diffusibility is lowered. The weight average molecular weight of the (1C) resin can be measured, for example, by GPC and using polystyrene as a standard. Examples of the above (1C) resin include the following compounds, and the softening point and weight average molecular weight thereof are within the above ranges. An aromatic diol represented by bisphenol A, bisphenol S, bisphenol F, bisphenol AD or the like, or a diol formed by modifying ethylene glycol, propylene glycol or alkanediol An aromatic polyglycidyl ether compound obtained by reacting with epichlorohydrin. a polyphenol type varnish resin, a polyphenolic phenolic resin or a copolymer thereof, and a polyphenolic phenolic resin or a copolymer thereof, and a polyphenolic varnish-type multi-shrinkage obtained by reacting with epichlorohydrin Glycerol ether compound. A glycidyl ether compound of a benzene dimethylphenol resin. Specific examples of the novolac type polyglycidyl ether compound include: a novolac type epoxy resin and a phenol novolak type epoxy resin. Specific examples of the aromatic non-polyglycidyl ether compound include: bisphenol A type ring gas, bisphenol F type epoxy resin, trisphenol-based epoxy resin, trisphenol 60 200900816 27285pif ethane type epoxy resin In the same manner as the number of epoxy groups divided by ^ G, it is preferable to use the amount of the epoxy group. This molecular weight has a gas bond than the resin; ΤίΓ. Calculate () c) The resin is the same. W key Lu this base! The method is also related to the (1B) ring, the reciprocal of the amount, so it can be determined by measuring (1C): the test amount, the following method is used to calculate the oxygen lanthanum solution and the static soil xane, adding hydrochloric acid - two consumption And calculated:;: (a) Na's liquid month and (1C) resin composed of a curable resin. The other two have *, wide 4 leakage, no (four) degree of balance, especially excellent tree (four) / 曰 ^ β) tree month and (1C) resin composed of hardening = month:,: sealant, its strength Especially excellent. Further, the liquid crystal sealing material □ having a curable resin composed of a seal and a J-tree is particularly excellent in leakage resistance. In addition, 'the liquid crystal sealing contains (1 Α) resin and (ic) resin; ', and the ratio of the resin is 5%, and the ratio of the resin is preferably (1A) resin: (lc) Resin = 7〇~97: 3 Bu 3. In the liquid crystal sealing W] 3, when (1A) tree and (1B) resin are used as the curable resin, the outline of such a tree is in terms of weight ratio, preferably (5) lion: (ib) 61 200900816 resin =10~70 ·· 90~30. When the liquid crystal sealing agent contains (ι) resin and C1 c) resin as the curable resin, the ratio of the ratio of the resins is preferably (1B) resin: (1C) resin = 7 〇 to 97: 3〇~3. When the liquid crystal sealing agent contains (1A) resin, (1B) resin, and (ic) resin as a curable resin, the ratio of such resins is preferably (1A) resin: (1B) resin. :(lc) Resin = 1〇~87 : 1〇~87 : 3~30.

The curable resin composition for liquid crystal sealing may further contain the above (5) epoxy curing agent, (6)% oxygen resin, and (7) in addition to the above (3) and 4)' (12). Photoradical polymerization initiator, thermoplastic polymer, (9) other additives. The details of these compounds and the like have been described above, and thus the description thereof will be omitted. 2. Method for Producing Curable Resin Composition for Liquid Crystal Sealing The curable resin composition for liquid crystal sealing of the invention can be arbitrarily produced within the range of not less than two, and for example, various methods are not particularly limited, and for example, Use two-leaf two-type: ^ well-known mixing machine. In order not to make the mixture condensate, it is = even hook, the temperature is better set to listen ~ pit: better and 丄: sink. Here, the idea of improving the stability of the composition's money is to use the smear of the smear and the bribes of the bribes and the bribes of the bribes (4). The liquid crystal display panel of the present invention can be produced by using the curable resin composition for wave-sealing of the present invention, and the following is a case where the liquid crystal display panel of the present invention is produced by sealing and filling the mixture with a glass plate 62 200900816 - I / Ζ δ ΐΓ ΐΓ ΐΓ 3. A good manufacturing method is explained. The method for producing a liquid crystal display panel is a method for producing a liquid crystal display panel by bonding a (four)_2 substrate with a curable resin composition for liquid crystal sealing, and comprising the steps of: 1) preparing a first substrate Step 'The second substrate includes a frame-shaped display region formed by the curable resin composition for liquid crystal sealing of the present invention so as to surround the pixel array region; 2) in the display region which is not cured, or another a step of dropping a liquid crystal onto a substrate; 3) a step of superposing the first substrate and a second substrate facing the substrate; and 4) a step of curing the resin composition for liquid crystal sealing by heating. 1) The step is to apply a liquid crystal sealing agent to any one of the two substrates, and prepare a substrate in which the frame-shaped display region is disposed. The frame-shaped display area means a seal shape drawn by this resin composition, which is also called a seal pattern. The substrate 疋 is a component of the display panel, and is usually composed of two glasses or the like. Examples of the two substrates used in the liquid crystal display panel include a glass substrate in which a TFT (thin film transistor) is formed in a matrix, and a color filter (c〇br fllter) and a black matrix (black matrix) are formed. The substrate. Examples of the material of the substrate include glass or 63 200900816 polycarbonate, polyethylene terephthalate, polyether PMMA (polymethyl methacrylate), and the like. .

An alignment film may be formed on the surface on which the respective substrates face. The alignment film is not particularly limited. For example, those produced by a well-known organic alignment agent or inorganic compounding agent can be used. Further, spacers may be scattered on the substrate in advance. St. ί often uses spherical cerium oxide particles, which can effectively maintain a ceU gap. Generally, it is possible to use an in-plane southerly material which is previously dispersed in the shape of the substrate L, or a spacer (external) in the liquid crystal sealing agent, which is not limited, and may be used according to the early gap. Size, while using well known people. Examples of the method of coating a liquid crystal seal on a substrate include: using a master pirate coating or a conventional technique by screen printing. In the case of manufacturing a small liquid crystal display, it is preferable to carry out coating by screen printing. In the region, or in another composition (4), the reaction is still cut. _ Gelation point Crystal drop can usually be carried out under the atmosphere. , k liquid The amount of dripping of the above liquid crystal is adjusted according to the size of the frame as compared with the β, ,, and A n of the cup. The ratio of the second is greater than the capacity of the capacity of the Sunplus (the unit) between the two substrates, so that the sealant that does not frame the space enclosed by the frame will not break. In addition, in the step of (2), in the step (2), when the liquid crystal is dropped on the substrate, the substrate is made heavy and W' can be dropped into the liquid crystal. Become the area of the display area. 3) The step is to overlap the substrate on which the liquid crystal is dropped with the other substrate. Since the substrate is bonded to each other by the difference in pressure, it is preferable to use a vacuum bonding apparatus or the like to overlap under reduced pressure. k a After the step 3), the step of superimposing 2 base atmospheric pressures may also be included. If it will be decompressed in the above way

:=, the difference in raw gas pressure, so the m is fed from the two base two pairs of substrates to bond the substrates to each other. Too much is the liquid that exists between the substrates. The liquid crystal sealing agent of this month can only be obtained by twisting: etc., the processing conditions of the liquid crystal (4) can be adjusted according to the composition of the liquid crystal (four) agent, and the liquid can be cured according to the county. ^In the case of 'the liquid crystal sealant can be temporarily hardened by light irradiation, the light can be irradiated' means the light of the application of the recording, the 曰, and the reaction (preferably the ultraviolet is the step of the panel only) In the case, the step 4) is preferably a step of hardening the liquid crystal sealing agent by heating. a force Γ Γ / Λ , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 13叱 and 3〇 minutes~12〇 minutes. In addition, when the light irradiation and the heat hardening are combined, the twisting stopper is preferably set to the thief to listen for 1 minute. Material = 65 200900816 In the above-mentioned case, it is possible to post-harden in minutes to 90 minutes as needed. L WC enters the lamp 30 and uses the following U thief towel to improve the production frame for the first step. After the lack of the liquid crystal sealant on the board, the liquid crystal sealant is used to form a plurality of bases or square substrates. The LCD will be post-fitted with two fit eyes. In the method, the liquid crystal display panels can be cut out by laminating the substrates to each other, and the liquid crystal display panel can be cut out. The group speed and the crystal light of the present invention can be accelerated only by heating. There is no hard by % two. ί, in addition, there are very few restrictions on panel design. In addition, the curing of the liquid crystal sealing agent does not require the use of an ultraviolet irradiation device or the like, and the manufacturing cost is low. Further, as the above-mentioned composition 1 to 』, or the liquid crystal sealing agent contains a predetermined thermal radical polymerization initiator, the liquid crystal sealing ship is heated from the free binary system. In a short time, hardening can be fully performed. Therefore, when the small panel m matrix or the wiring = liquid crystal display panel mounted on the mobile phone is used, there is no uncured portion in the light shielding portion. The so-called black matrix refers to the photoresist (photoresist). B ^ surrounds the checkered frame of the three primary colors R (red) G (green) indigo constituting the light of the color grading sheet. Further, the means for applying ultraviolet rays or the addition means is not particularly limited. An example of a heating device usable in the present invention, a hot pot, a hot plate, a hot press (hot 66 200900816 z/j, ^pn press ), according to the above method, using the present invention The liquid crystal display panel is composed of a curable resin for liquid crystal sealing, and the liquid crystal display panel is excellent in smear leakage, and can suppress ink crystal dyeing, and the cured material of the liquid crystal sealing agent is entangled with the substrate, so that the display characteristics are good. [Examples; |

The present invention is exemplified by the following examples and comparative examples, and the present invention is not limited to the embodiments shown herein. In addition, "%" and "parts" as disclosed below mean "= parts". In the first embodiment, a comparative example and a comparative example of the curable resin composition for liquid crystal sealing of the present invention will be described. (1) Acrylic resin, the use of the material used in the comparison of the materials used in the 1-1 to 13 and the comparative examples 1 to 4, and the use of the age of the squid, _ ultrapure water, repeat the above steps 12 times and high. Purification treatment.彳Acrylic resin i: bisphenol oxime type epoxy resin (3〇〇2A: manufactured by Kyoeisha Chemical Co., Ltd., molecular weight _) 夂酉曰 夂酉曰 烤 烤 酸 2 2 2 2 2 2 2 2 2 2 2 2 2 2 n (2) modified epoxy resin in the 485) is prepared by borrowing (four) sputum synthesis _ oxygen dragon (synthesis 67 200900816 [synthesis example I -1] installed with a mixer, air duct, thermometer, cooling tube 〇 60 g of bisphenol F-type epoxy resin (E ^ YDF-8170C: manufactured by Tohto Kasei Co., Ltd.), 36 g of acrylic acid, diethanolamine, and heated at 1 UTC under a dry air flow. The acrylic modified epoxy resin was obtained by stirring for 5 hours. The obtained lipid was washed 12 times with ultrapure water. '曰 The following raw materials were prepared: (3) Thermal radical polymerization initiator Thermal radical polymerization initiator 88 : 1,1-azobis(2,4-cyclohexane small carbonitrile) (V-40: manufactured by Wako Pure Chemical Industries, 10 hour half-life temperature is thermal radical polymerization initiator 75: 2-ethyl peroxide Tripentyl hexanoate i^Lupasol 575 : manufactured by API Corporation, 1 hour half-life temperature thermal radical polymerization initiator 65 : 2,2'-azo (2_mercaptopropionate) (V_601 'made with Wako Pure Chemical Industries, 1 hr half-life temperature is 65 ° c) Thermal Radical Polymerization Starter 51: 2,2'-Azobis (2.4-didecyl) Valentonitrile) (V·65 · Wako Pure Chemical Manufacturing, 1 hour half-life temperature is 51. (:) (4) Filler Filler 1. Spherical Oxidized Oxide (Seahostar S-30: 曰本制制制' Average = secondary particle size is G.3, specific surface area is 11 m2 / g) Filler 2. Spherical yttrium oxide (SO-C2: ADMATECHS company average _ human particle size is 〇 · 9 / zm, specific surface area is 4m2 / g) (5) % oxygen hardener 68 200900816 27285ρΐί Latency ί 氧 oxygen hardener 1 :] ^ HE , Λ . ^, 3-bis(indenylethyl)-5-isopropylhydantoin ( Amicure VDH : 4 ^ Ajinomoto company, melting point of 12 〇. 〇 and 八一制i & agent 2. Diterpene adipate (ADH: manufactured by Otsuka Chemical Co., melting point 181. 匸) ' (6 Epoxy Resin r2 Oxygen Resin / : 邻甲盼 jun varnish type solid epoxy resin (EOCN-1020-75: Nippon Kasei Co., Ltd.% 士^ 4 兀 公司 company, 赭 measured by the method of the world

The weighting point is 75 ° C, epoxy equivalent is 215 g / eq) Epoxy resin 2: double-test A-type epoxy tree, epoxy equivalent of 190g / eq) (7) photoradical polymerization initiator Photoradical polymerization initiator: 1:1-cyclohexylphenyl fluorene (Irgacure 184. manufactured by Ciba Speciality Chemicals) Photoradical polymerization initiator 2: 2,2-dimethoxy-2-phenylbenzene Ethyl ketone (Irgacure 651: manufactured by Ciba Speciality Chemicais) (8) Thermoplastic polymer alkyl methacrylate copolymer microparticles (F_325: manufactured by Zemun Corporation, Japan, having an average primary particle diameter of 0.5 vm). [Evaluation method] The evaluation methods performed in Examples I-1 to 13 and Comparative Example _丨~4 will be described. Here, i) the viscosity, u) the leakage resistance of the liquid crystal sealing agent, iii) the coating property of the liquid aa sealant, and the subsequent strength were evaluated for the properties of the liquid crystal sealing agent. The details of each measurement evaluation method are as follows. i) Viscosity measurement 69 200900816 An E-type rotary viscometer (digital rheometer, ULTRA, manufactured by BROOKFIELD) and a half D H _ m degree of 3 were used. The CP-52 type cone-plate type sensor is measured at the following rotation speed of the coffee and the angle rpm. The viscosity of the cattle under 1.0 pit was measured by placing the liquid crystal of the present invention for 5 minutes. , 25C, the viscosity at 8 ° C: the liquid crystal sealing of the present invention

In the cup of the rotary viscometer, the temperature was raised at a heating rate of 5 t/min to the order, and the measurement was carried out after standing at 80 ° C for 5 minutes. In the above-mentioned measurement method, when the liquid crystal sealing agent cannot be measured when the _ exceeds the measurement limit, the measurement is performed using the viscosity (RheoSt surface RS150: manufactured by HAAKE). The measurement of the plate method is based on the standard method of the above-mentioned model. Immediately after the temperature was raised to 80 ° C, the measurement was carried out. k ii) Leakage resistance of liquid crystal male sealant using a dispenser (sh〇tmaster • Musashi Engineering (M job hi Engi sing) company), will add i parts of 5 _ (glass fiber) The liquid crystal sealing agent was drawn in % on a 4 〇 (4) surface glass substrate (RT-DM88PIN: EHC) with a transparent electrode and an alignment film at a line width of 〇5 mm, a thickness of %, and a m. Frame shape of mm x 40 mm. The liquid crystal material (MLC-11900-000: manufactured by Merck Co., Ltd.) having the same amount of panel content as the bonded panel was precisely dropped by a dispenser. Next, the opposing glass substrates were superposed under a reduced pressure of 9 〇Pa, and 70 200900816 27285pif was returned to atmospheric pressure, and then heated at 120 ° C. Hardness was performed. (4) Liquid tightness The sealing linearity of the panel was based on the following criteria [ , the ratio of the maximum width to the minimum width of the seal]% ^ The most expensive biliary (four) maximum width read] X100 The ratio is greater than or equal to 95%: 〇 (excellent)

The above ratio is 50% or more and less than 95%, and the above ratio is less than 50%: >< (Poor) The coating property of the liquid crystal sealing agent is added with a liquid crystal sealing of 1% of 5 //m glass fiber The agent is filled into a syringe (syringe) with a needle of 4 mm in the needle. Then, using a dispenser (Shotmaster: manufactured by Musashi Engineering Co., Ltd.), at a discharge pressure of 0.3 MPa, a coating thickness of 20 /zm, and a coating speed of 10 〇mm/sec, at 3〇〇_x4 〇〇mm LCD panel

The load was applied to fix it for 60 minutes. On the glass substrate (manufactured by Sakamoto Electric Glass Co., Ltd.), five frame shapes of 35 mm x 40 mm were drawn. The seal shape of the drawn seal pattern was evaluated according to the following criteria. The frame shape of the seal is not broken at all, and the sealing frame is 48 to 50: 〇 (excellent) The above frame shape is less than 45 to 48: △ (slightly superior) The above frame shape is less than 44: X (poor ) iv) Next strength 71 200900816 On a 25 mm x 45 mm x 5 mm thick alkali-free glass (n〇_alkali glass), a liquid crystal sealant with 1% of 5 glass fibers is screen-printed to a diameter of 1 mm. Round, attached to the same glass, and fixed on one side, and then heated at 12 (rc for 1 hour to make a test piece. Using a tensile tester (m〇del21〇: manufactured by Intesc〇)) The tensile strength of the test piece was measured in a parallel direction = 2 at a speed of 2 mm/min. The strength was evaluated according to the following criteria. () Tensile strength: 10 MPa or more: 〇 (excellent) Tensile strength 7 MPa or more and less than 10 MPa : △ (slightly excellent) Tensile strength less than 7 MPa : X (poor) [Example I -1] In a mixed state, 30 parts of acrylic resin, 70 parts of synthetic work q Obtained methacrylic acid modified epoxy resin, 〇1 hour half-life temperature The thermal radical polymerization initiator having a degree of 75 ° C, 2 parts of filler i pre-I: ready to mix, and secondly, the solid raw material is kneaded by three rolls until it reaches 5 // m or less. This composition was filtered with a mesh aperture of 1 〇 from a melon filter (MSP-10-E10S: manufactured by ADVANTEC Co., Ltd.), and then subjected to vacuum defoaming treatment to obtain a liquid crystal sealing composition. The viscosity of the resin composition for liquid crystal sealing at 25t is 260 Pa.s at 〇·5 rpm '18 〇Pa.s under i 〇, 120 Pa's at 5 。. 72 200900816 27285pif The viscosity measured by the E-type rotary viscometer at 80 C is greater than

'The result of the parallel plate method (Rhe〇Stress RS150: HAAKE system 1) is 9.00E + 05 Pa.s. In addition, the thixotropy index is 2.2, and 'by the above evaluation method, for liquid crystal sealing The resin composition was subjected to t-type failure, and its characteristics were evaluated. [Comprehensive Example ~ 13]

In the same manner as in the case of Example 1-1, the resin composition for the seal of the liquid crystal seal shown in Table 2 was obtained. Further, the same evaluation as in Example 1-1 was carried out. [Comparative Example; [-1 to 2] 曰^ίΓ In the same manner as in Example 1, a liquid crepe blanket m composition of the composition shown in Table 3 was obtained. And the same evaluation as in the example was carried out. [Comparative Example I-3] 60 parts of propylene grease 2, 4 parts of epoxy resin 2 were mixed and mixed by a line-type mixing device. 9 Second, add 2 parts of photoradical polymerization initiator in this resin, VIII, -π, face polymer, 1 part of pour coupling agent (s5ig: chiss〇y = i, 10 parts of filler 2, 1G part of latent The epoxy curing agent 2 was mixed by means of a device, and then mixed with a ceramic grinder to obtain a resin composition for liquid crystal sealing. The obtained Wei composition was compared with Example 2 [Comparative Example I-4] In a lamp star-type mixing device, 60 parts of two dilute acid trees, 2, 4 parts of epoxy 73, 200900816 resin 2 were mixed and stirred. Next, the resin was further blended into the resin. 10 parts of a thermoplastic polymer, 1 part of a decane coupling agent (S510: manufactured by Chisso Co., Ltd.), 10 parts of a filler 2, and 10 parts of a latent epoxy curing agent 2, which were mixed and stirred by a planetary stirring device. The mixture was further mixed with a grinder to obtain a resin composition for liquid crystal sealing. The obtained resin composition was evaluated in the same manner as in Example 1. The examples I-1 to 13 and Comparative Examples I-1 to 4 were used. The prepared liquid crystal drip is leaky, coatable, and connected to the technical sealant. The results of the strength are shown in Table 1 to Table 3. 200900816 27285pif [Table l]

- Example 1-1 Example 1-2 Example 1-3 Example 1-4 Example 1-5 Example 1-6 Composition of acrylic resin 1 30 30 25 25 25 25 2 — — — — — — Synthesis Modified epoxy resin 70 70 70 70 70 70 Thermal radical polymerization initiator 88 — — — 1 — — 75 1 0.02 2 — 1 — 65 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — A — Filling material 1 20 20 20 20 20 20 2 — — — — — — epoxy hardener 1 — — — 5 5 5 2 — — — — — — Epoxy resin 1 — — 5 5 5 5 2 — — — — — — Photoradical polymerization initiator 1 — — — — — — 2 — — — — — Thermoplastic polymer — — — — — viscosity — 25〇C/〇.5 rpm (Pa-s) 260 260 320 450 450 450 25〇C/1.〇rpm (Pa-s) 180 180 250 275 275 275 25〇C/5.0rpm (Pa-s) 120 120 150 180 180 180 80°C/l.〇rpm (Pa- s) Measurement limit 650 Determination limit 760 Measurement limit Measurement limit Viscosity at 80 ° C measured by the parallel plate method (Pa's) 9.00E + 05 3.5E+ 03 9.00E + 05 3.5 E+ 03 9.00E + 05 9.00E + 05 Thixotropic index 2.2 2.2 2.1 2.5 2.5 2.5 Evaluation (0 leakage resistance 〇Δ 〇Δ 〇〇(ii) coatability 〇〇〇〇〇〇(m) followed by strength〇〇 〇〇〇〇75 200900816 [Table 2]

EXAMPLES I-7 Examples I-8 Examples I-9 Examples I-10 Examples I-11 Examples I-12 Examples I-13 Composition Acrylic Resin 1 25 30 30 25 100 — 25 2 — — — — — — — Modified epoxy resin 70 70 70 70 — 100 70 Thermal radical polymerization initiator 88 — — — — — — 75 — — — — 1 1 — 65 — — — — — — — 51 1 1 1 1 — — 1 Filling material 1 20 5 45 20 20 20 10 2 — — — — — — — Epoxy hardener 1 5 — — 5 — — 5 2 — — — — — — — Oxygen Resin 1 5 — — 5 — — 5 2 — — — — — — — Photo-radical polymerization initiator 1 — — 1 — — — 2 — — — — — — — Thermoplastic polymer — — — — — — 10 Viscosity 25〇C/0.5 rpm (Pa-s) 450 80 1050 450 500 100 480 25〇C/1.〇rpm (Pa-s) 275 70 480 275 400 60 290 25〇C/5.0rpm (Pa*s 180 65 250 180 300 40 240 80°C/1.0 rpm (Pa-s) Measurement limit measurement limit measurement limit measurement limit measurement limit measurement Limit of measurement limit Viscosity at 80 ° C measured by the parallel plate method (Pa-s) 9.00E + 05 5.00E + 05 9.00E + 05 9.00E + 05 9.00E + 05 5.00E + 05 9.00E +05 Thixotropic index 2.5 1.2 4.2 2.5 1.7 2.5 2.0 Evaluation (ί) Leak resistance 〇〇〇〇〇〇〇 (ii) Coating properties 〇〇 〇〇〇〇 iii (iii) Then strength 〇〇〇〇〇 Δ 〇76 200900816 27285pii [Table 3]

^ Comparative Example 1-1 Comparative Example 1-2 Comparative Example I-3 Comparative Example 1-4 Composition Acrylic Resin 1 25 30 — 2 — — 60 60 Modified Epoxy Resin 70 70 obtained in Synthesis Example 1 — Thermal Radical Polymerization Starter 88 — — — 75 — — — 65 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — 10 10 氧氧树月曰1 5 — — — 2 — — 40 40 Photoradical polymerization initiator 1 1 — — — 2 — — 2 — Thermoplastic polymer — 10 10 Viscosity 25〇C/〇.5 rpm (Pa*s) 450 1390 243 310 25〇C/1.〇rpm (Pa-s) 275 530 250 370 25〇C/5.0rpm (Pa*s) 180 275 255 400 80°C/l.〇rpm ( Pa-s) 380 Determination limit 270 350 Viscosity at 80 ° C measured by the parallel plate method (Pa.s) 2.9E+03 9.00E+05 6.0E + 02 8.0E+02 Thixotropic index 2.5 5.1 1 1.3 Evaluation (i) Bubble leakage X 〇 XX (ii) Coating property 〇 X 〇〇 (iii) Next strength 〇〇 XX The liquid crystal sealing agent shown in Examples I-1 to 13 has leakage resistance. Coating property, Then the strength is excellent. When these examples were compared with the results of Comparative Examples I-1, 3, and 4, it is clear that when the viscosity of the liquid crystal sealing agent at 80 ° C is 500 Pa's or less, the leakage resistance is produced. problem. Further, when the examples were compared with Comparative Example 1-2, it is understood that if the viscosity at 25 ° C and 1.0 rpm is more than 500 Pa·s and the thixotropic index is more than 5, the coating property is improved. cause problems. Further, from the results of Examples I -1 77 200900816 to 13 and Comparative Examples I -3 and 4, it is understood that if the content of the filler is small, there is a problem in the subsequent strength. Next, examples and comparative examples of the curable resin composition n for liquid crystal sealing of the present invention will be described. [Examples 1 -1 to 6, Comparative Examples η _ ι, 2] The materials used in the respective examples and the like are as follows. (3) Thermal radical polymerization initiator

Thermal Radical Polymerization Starter: 2,2,_Azobis(2_methylpropionate Κ Trade Name: V-601' and Wako Pure Chemical Manufacturing, 1 〇 half-life temperature ° (4) Filler Filler Spherical oxidation; Sea 〇 ( (Seah〇starS-30: manufactured by Nippon Shokubai Co., with an average-order particle size of 0.3 and a specific surface area of u (5) Epoxy hardener: Thermal latent epoxy hardener: 1, 3·Bis(decyl-ethyl)_5•Imimethacin (Amicure VDH: Furuo Goto 8] 1 ^ ^ ethane acetoin, melting point 12〇γ ^ (6) epoxy ring Epoxy resin measured by the oxygen resin ball method. The adjacent acetal varnish type solid (EOCN-1020-75: manufactured by Nippon Kayaku Co., Ltd., with a softening point of the ring of 75 ° C and an epoxy equivalent of 215 g / eq) (9) Other additives base three - (10) Free radical curable resin with toluene _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Resin. Here, the radical scavenging property 2 described below is a resin synthesized by the following synthesis example π • 1. Free radical curable resin 1 · Double age Α epoxy Aliphatic acid modified dipropyl women unitary purpose (Class 2A ·· manufactured by Kyoeisha Chemical, molecular weight _)

Free radical sclerosis lion 2 : 1 molecule (4) (meth)acrylic acid modified epoxy resin having epoxy group and (meth) acrylonitrile group [Synthesis Example Π-1] A mixer, an air pipe, a thermometer, and the like are attached. A 500 ml four-necked flask of a cooling tube was charged with 160 g of bisphenol F-type epoxy resin (Ep〇t〇ht〇YDF-8170C, manufactured by Tohto Kasei Co., Ltd.), 36 g of acrylic acid, and ruthenium diethanolamine. Under air flow, the mixture was heated and stirred at 11 (rc for 5 hours to obtain an acrylic modified epoxy resin. The obtained resin was washed 12 times using ultrapure water. 曰β (11) radical transfer agent radical chain transfer agent 1:1,3,5-tris(3-mercaptobutoxyethyl)_135_triazine-2,4,6(111,3's 511)trione (〖&代1^1^0^尺- 1: manufactured by Showa Denko Co., Ltd. (Wako Pure Chemicals Free radical chain transfer agent 2: tetraethyl thiuram disulfide industrial manufacturing) Free radical bond transfer agent 3: Diethoxy oxime polycarbon bond poly person (Thiokol LP -2 : manufactured by Toray Fine Chemicals Co., Ltd.) Free radical chain transfer agent 4: Third-dodecyl mercaptan [Evaluation method] 79 200900816 For the examples Π-1 to 6 and the comparative examples nq, 2 Evaluation methods will be described. Here, the measurement i) of the liquid crystal display panel, a liquid crystal sealing sealant, III) followed by the strength of the cured sealant liquid crystal, the characteristics of the liquid crystal sealant was evaluated. The details of each measurement evaluation method are as follows. 0 The display of the liquid crystal display panel uses a liquid crystal sealant to which 1% of 5, glass fiber is added, with a line width of 0.5 mm and a thickness of 50, on a 40 mm x 45 mm glass substrate with a transparent electrode and an alignment film ( On the RT_DM88pm ^Hc company, draw a frame of 35 mm x 40 mm. Drawing was performed using a dispenser (Shotmaster: manufactured by Musashi Engineering Co., Ltd.). Next, a liquid (MLC-6848-000, manufactured by Merck), which is equal in amount to the panel contents after the bonding, was precisely dropped by a dispenser. Then, after the two glass substrates were overlapped in a relative manner under a reduced pressure of 90 Pa, the load was fixed by applying a load, and then returned to atmospheric pressure from a reduced pressure: the substrates were subtracted from each other. Further, the laminated plate was placed in a circulating oven at 70. After heating under the arm for 30 minutes, the film was further heated at 12 Torr for 60 minutes to cure the liquid crystal sealing agent. The two films on the two substrates of ΐ, 贴 δ are attached with a deflecting film, respectively, and are formed into a liquid crystal display panel. The liquid crystal display panel is driven by applying a voltage of V to the liquid crystal display panel with a DC power supply device. At this time, visual observation of the liquid crystal display function in the vicinity of the sealed seal formed by the two crystal seals is often performed, and the display function of the display of the liquid crystal display panel 80 200900816 27285pii to the vicinity of the sealed boundary is exhibited according to the following criteria. : 〇 (good display property) The case where the display function is not exhibited from the vicinity of the sealing boundary to a distance of more than 0.3 mm: X (significantly poor display property) ii) Sealing property of the liquid crystal sealing agent and the manufacturing method of the above liquid crystal display panel The same method, the case" for three LCD panels, according to the criteria shown below, in four levels

The sealing property of the frame (sealing) which becomes the display area on each liquid crystal display panel was evaluated. ^ There is no main seal (main seal) damage, and there is no case where the liquid crystal is sealed to the green "HnO (hereinafter referred to as insert): ◎ Although the insertion is visible, there is no damage to the main seal: one of the main seals is damaged: △ There are 2 or more places where the main seal is broken: χ m) The adhesion strength of the hardened liquid crystal sealant, /兀u melon·π mmx thickness 5 mm, the alkali-free glass is 5^ The liquid crystal sealant of the fiber is screen-printed, and P 15 is clamped to the above-mentioned two-folded 7^^======================================================================== ^The next minute is the Si piece formed by hardening the liquid crystal sealant only by heating. 81 200900816 ^ By using a tensile tester (model 210: manufactured by Intesco), the speed of t 2 mm/min The obtained test piece was taken in a direction parallel to the bottom surface of the glass to measure the plane tensile strength. Then the strength was evaluated according to the following criteria: When the tensile strength was 10 MPa or more: 〇 (following the strength) & When the tensile strength is less than 10 MPa: X (and subsequent strength difference) iv) The viscosity stability of the sealant was measured by an E-type rotary viscometer (manufactured by BROOKFIELD Co., Ltd.: digital rheometer, Wei: DW ULTRA), and the viscosity stability of the liquid crystal (four) agent prepared by the following method was measured. The viscosity of the liquid crystal sealing sword is just after the preparation of the 'muchness' and the viscosity after 5 days of storage under the pit. The measurement is a cp_52 cone-plate type sensor with a radius of 12rnm and an angle of 3. The rotation speed is set to 2·5 rpm. The viscosity of the liquid crystal sealing agent measured was set to 1 after the preparation, and the viscosity after storage for 5 days at 25 C was set to π 2 , and the liquid crystal sealing agent was used according to the following criteria. Evaluation of viscosity stability. Case where the value of 7?2/t?1 is less than 15: The value of 〇t/2/t? 1 is greater than or equal to 15 and less than 2 ··· △ 7/2/7? When the value is greater than or equal to 20: χ [Example Π-1] 15 parts of peroxy resin and 45 parts of radical curable resin were dissolved by heating at 10 (TC for 1 hour to prepare a uniform solution. Secondly, After cooling this solution, 'add 2 parts of the free radical 82 obtained in the above synthetic example ^ 200900816 27285pif hardening tree 2, 0.5 part of the free radical chain transfer agent, i5 parts of the filler, 3 parts of the latent epoxy hard _, and 丨 part as a fine intermixing agent, mixed with a mixer, and then _ three (four) line mixing, Until the solid raw material reaches 5 //m or less. Then, using a mesh pore size of 1〇/zm; the mixture is filtered (MSP-10-E10S: manufactured by ADVANTEC), and the mixture is filtered, and then 5 parts are added. After the thermal radical polymerization initiator, vacuum agitation and defoaming treatment was carried out using a planetary mixer to prepare a liquid crystal sealing agent.

[Example Π - 2] A liquid crystal sealing agent was prepared in the same manner as in Example jj-1 except that the radical chain transfer agent 2 was used. [Example Π-3] A liquid crystal sealing agent was prepared in the same manner as in Example π-1 except that the radical bond transfer agent 3 was used. [Example Π-4] The radical curable resin 1 was set to 42.5 parts, the radical curable resin 2 was set to 15 parts, and the radical chain transfer agent 1 was set to 25 parts, and the filler was set. A liquid crystal sealing agent was prepared in the same manner as in the example π-ΐ except for 20.5 parts. [Example Π-5] The radical curable resin 1 was set to 48 parts, the radical curable resin 2 was set to 15 parts, and the filler was set to 22 parts, and the epoxy resin was set to 10 parts. The liquid crystal sealant was prepared in the same manner as in Example Π-1. 83 200900816, [Example -6] A liquid crystal sealing agent was prepared in the same manner as in Example Π-1 except that the radical chain transfer agent 4 was set to 0.5 part. [Comparative Example Π-1] The radical curable resin 1 was used in an amount of 45.5 parts, and the radical curable resin 2 was set to 20 parts, except for the case where the radical chain transfer agent was not used at all. A liquid crystal sealant was prepared in the same manner as -1. [Comparative Example 2] A liquid crystal sealing agent was prepared in the same manner as in Example Π-1 except that the thermal radical polymerization initiator was not used and the radical curable resin 1 was changed to 45.5 parts. The amount of each component of the liquid crystal sealing agent used in each of the examples and the comparative examples, and the evaluation results of the sealing property, the bonding strength of the liquid crystal sealing agent to be prepared, and the display property of the liquid crystal display panel using the same are summarized. Shown in Table 4. 84 200900816 27285pif [Table 41

= Table 4 is clear: 4: The liquid Japanese-Japanese male sealant of the examples n] to 6 invented in the present invention is applied, and the above-mentioned sealing property and the above-mentioned sealing property are different. "The upper entrance strength and displayability are very good."

4 of -1', when not using a radical chain transfer agent, is sealed by a comparative example; Further, when a thiol-based agent is used, it is possible to improve the secondary simplification as a thermosetting property of the thermophilic agent, and it is more stable than the use of the thiol. On the other hand, there is a problem in that the heat is not used in the dense; = strong; the ratio of the strength of the connector and the aspect of the invention are the same [Examples mi~6, below the core of the comparative example, the liquid crystal sealing of the present invention In the examples and comparative examples which were carried out with the curable resin composition, the materials and the like used in the detailed description are as follows: [Examples 1 to 6 and Comparative Examples 冚_1 to 4 are prepared] The materials used are shown as D. (3) Thermal Radical Polymerization Initiator Thermal Radical Polymerization Starter 1: 2, 2L Oxygen Double (2 copies of 2 (V-65: manufactured by Wako Pure Chemical Industries, 10 hours half-life temperature is H, starting temperature is 51). 〇

Thermal Radical Polymerization Initiator 2 : 2,2,·Azobis(2-methylpropionate) (Individual: Made by Wako Pure Chemical Industries, 1 () hour half-life temperature is 66 = fever start temperature is 60 ° C) Thermal Radical Polymerization Initiator 3 : Peroxide 2 · Ethylhexanoic acid Third pentylene (Lupasol 575: manufactured by API Corporation, 10 hours half-fat ^ is 75.0:, the onset temperature of heat is 88 Thermal Thermal Radical Polymerization Starter 4 : u_Azobis(2,4_cyclohexane-small carbonitrile) UerhexylO. Made by Nippon Oil & Fat Co., Ltd., 1 hour half-life temperature is 70 C, and the onset temperature is 1 〇5.匚) (4) Filler filler 1: spherical cerium oxide (Seah〇star s_3〇: manufactured by Nippon Shokubai, average-secondary particle size is .3 //m, specific surface area is llm2/g ), 真充才斗2. Spherical dioxide dioxide (SO-C2: ADMATECHS company, 1 particle size G 9 , specific surface area 4m2 / g), filling 3. Spherical dioxide Shi Xi (s〇_ci : aDmatechs company wept average granules of 0.25 〃m, specific surface area A17_4m2 / g) 86 200900816 272^pii Filler 4: talcum powder (SG-2000: manufactured by Sakamoto Talc The average primary particle size is 1.0 ym and the specific surface area is 36.6 m2/g. (5) Epoxy hardener latent epoxy hardener 1: 1,3-bis(decylcarbonylethyl)-5-isopropyl Amidourin (Amicure VDH: Ajinomoto Fine-Techno, melting point: 120 ° C) Latent epoxy hardener 2: Diterpene adipate (ADH: manufactured by Otsuka Chemical Co., Ltd., melting point 181. (: ) Latent epoxy hardener 3 : Amicure PN-23J (Ajinomoto Fine-Techno, melting point l〇5 ° C) (7) Photoradical polymerization initiator photoradical polymerization initiator 1· : 2,2-dimethoxy-2-benzyl acetamidine (Irgacure 651: manufactured by Ciba Speciality Chemicals) (8) Thermoplastic polymer alkyl methacrylate copolymer microparticles (F-325: manufactured by Zeon Corporation, Japan) , average primary particle size is 0.5 //m) (9) Other additive coupling agent 1: decane coupling agent (S-510: manufactured by Chisso Co., Ltd.) Coupling agent 2: decane coupling agent (KBM-403: manufactured by Shin-Etsu Chemical Co., Ltd.) 12) The curable resin is appropriately selected from the following (1A) resin, (1B) resin, and (1C) resin. (1A) Resin (radical difunctional resin) 8 7 200900816 A· 1 A ii resin (A- ι) The resin resin CA-2) synthesized in Synthesis Example m-1 is described as follows: The resin resin synthesized in Synthesis Example m-2 is described (A- 3): The resin resin (A-4) synthesized in Synthesis Example 羾-3 is described as follows: The resin resin (A-5) synthesized in Synthesis Example 111-4 is described in detail. Resin resin (A-6):: Di-alkali A plastic diacetic acid epoxy vinegar resin (A-7): Resin synthesized in Synthesis Example ffi_6 (1B) Shuyue (': Resin (B-1): A description of the pheno-ether-type partially acrylylated cycloolefin resin (B-2) synthesized in the synthesis example, the bisphenol F type synthesized in the following Synthesis Example 羾-8 Part C: fcfp acid-based epoxy resin ruthenium resin (B-3): resorcinol diglycidyl (4) partially synthesized in the following synthesis example melon-9 -4): Resin resin (B-5) synthesized in the following Synthesis Example 羾-10: Resin () resin synthesized in the following Synthesis Example 羾-11 (B_6): The following synthesis example dish ~12 Synthetic resin (1C) resin resin (C-1): o-fphenol novolac type solid epoxy resin (commercial product) Lipid (C-2): Bisphenol A type of earth-alkali resin (commercial product) Shuyue (C-3) (compared to car) A-type epoxy resin (commercial product) [analysis of tree wax In addition, in order to provide the quality of the resin synthesized in the synthesis example, etc., 88 200900816 27285pif, a θ, a, υ epoxide equivalent m measurement and oxidation measurement epoxide are appropriately performed according to the following method. It is calculated by the method of sputum: after the resin is dissolved in hydrochloric acid and milk sputum, it is consumed by the epoxy group.

2) Determination of acid value I line measurement. First, the resin is dissolved in a resin solution. A solution of ph__alem ethanol was added to the resin solution. Then, the resin solution was dropped into an amount of 0.1 equivalent of Krw aw " consumed by the ethanol solution; and the solution was changed to colorless before [synthesis example Π -1] radical 'one S-energy resin (Α -1) Synthesis of a flask equipped with a thermometer, a cooling tube, and a mixing device. The flask was charged with 170 g of double enzyme F digoxime _ (manufactured by Dainippon Ink Chemical Industry Co., Ltd., Epiclon 830S, epoxy equivalent of 17 at 9 (after TC was scrambled for 2 hours, then one side ^- The mixture was stirred for 3 M and occasionally reacted. Thereafter, the reaction solution was washed with a rail of water, and then the toluene was removed to obtain a resin. The obtained tree had a number average molecular weight of 457 and a peak of 2 in the molecule. Therefore, the hydrogen-energy basis is calculated. The tree (four) structure obtained by this synthesis example is 89 200900816

[Synthesis Example ΙΠ-2] Synthesis of a radical difunctional resin (A-2)

Prepare a flask equipped with a thermometer, a cooling tube, and a stirring device. The flask was charged with 200 g of Epiclon 850 CRP (bisphenol a-ring &; ^ manufactured by Otsuka Ink Chemical Co., Ltd.), 丨〇〇g methyl decanoic acid, resin: benzene, 0.4 g of triethylamine, 0.4 g of The methoxy phenol is mixed with a § 曱 mixture and then reacted downstream of the thief M. The mixture was cleaned and washed with a f-column, and the resin obtained by 100% of the methacrylic acid thiolated tree homogenate 513 was averaged by GPC. The molecular weight is a peak/peak. Since the obtained tree month is intended to have 2 wind bond functional groups in the molecule, the amount is calculated as 3.9 secret 3 -> he. The structure of the resin to be served by the jin is as follows.

(A-2) [Synthesis Example m-3] Radical difunctional resin 200900816 27285pif A flask equipped with a thermometer, a cooling tube, and a stirring device was prepared. The flask was charged with 117 g of a mono-glycidol scale (Denacol EX-201 'epoxide equivalent 117 eq/g manufactured by Nagase ChemteX Co., Ltd.), 79 g of acrylic acid, 500 g of benzene, and 1 g of the third The butyl ammonium bromide was stirred to form a homogeneous solution. This solution was taken at 9 Torr. After stirring for 2 hours, the mixture was further returned to 6 lL, and allowed to react for 6 hours. Thereafter, after washing the reaction solution with ultrapure water, the benzene was removed to obtain a resin. The obtained resin was obtained from GPC and had a number average molecular weight of 366 Å whose peak was a single peak. Since the obtained resin had two radicals in the molecule, the amount of the hydrogen bond functional group was calculated to be 5 46 χ妒mQi/g. The structure of the resin obtained in the present synthesis example is as follows.

[Synthesis Example m-4] ......^ '5) Synthesis of a radical difunctional resin (A-4) A thermometer (10) g of a benzene-epoxy resin flask was placed in a thermometer, a cooling tube, and a flask. In this case, Oxygen hw 1 § as a polymerization inhibitor, the antimony milk of G.2g as a reaction catalyst is stirred, and a uniform solution is prepared to form a uniform solution g: Rare: 500 into the air' - This solution was applied to 8Q. The surface of the flask was refluxed, and the surface was mixed for 36 hours to make it = (1), hour, and further 200900816. Thereafter, after washing the reaction mixture with ultrapure water, the resin which was propylated was removed. The number average molecular weight of the obtained GPC is 459, and the resin of the ruthenium has two radicals in the molecule, and the hydrogen bond functional group J is, for example, 4.36 χ 1 〜g. Resin obtained by this synthesis example ‘

[Synthesis Example m-5] Synthesis of Radical Bifunctional Resin (A-5) A flask equipped with a thermometer, a cooling tube, and a stirring device was prepared. The flask was charged with 296.2 g (2 moles) of phthalic anhydride and 917 〇 g (2

Moer) 6-caprolactyl adduct of 2-acrylic acid 2-pilycolic acid (piaccei fa3, molecular weight: 459 g/mo, manufactured by Daicel Chemical Co., Ltd.), triethylamine, 0.9 g of hydroquinone , to mix. The reaction mixture was then stirred at 11 Torr to react. The reaction was carried out while monitoring the acid value of the reaction mixture. When the acid value of the reaction mixture reached 48 mgKOH/g, the reaction temperature was 90 °C. Next, 680.82 g (2 mol) of bis-A diglycidyl scale and 1.6 g of tetrabutylphosphonium bromide were added to the reaction mixture, and the reaction was carried out at 90 ° C until the acid value of the reaction mixture reached 2 mg KOH / g. until. Thereafter, 144.1 g (2 mol) of propyl 92 200900816 27285 pif enoic acid and 1.8 g of p-diphenol were further added to the reaction mixture, and air was supplied to the flask, and the reaction was carried out for 2 hours at 8 ° C. 'And then raise the temperature to the thief and continue the reaction. The reaction is carried out until the acid value of the reaction mixture reaches 2. The mixture after completion of the reaction was washed with ultrapure water and refined by a column to obtain a resin. This resin is a glycerol group of bisphenol A diglycidyl ether and a 6-heximide adduct of the acrylonitrile 2

A resin obtained by reacting a mercapto group of a compound formed by the reaction of phthalic anhydride into a reaction between the other glycidyl group of bisphenol A monoglycidyl ether and a carboxyl group of "acrylic acid". The resin of the present synthesis was determined by GPC, and as a result, the peak was a single peak and the molecular weight was 1〇〇5. Since the obtained resin has two hydroxyl groups in the molecule, the amount of the hydrogen bond functional group is calculated to be 1.99xl0-3 mol/g. The radical difunctional resin (A-6) bisphenol A type epoxy acrylate (EB37 〇〇: manufactured by DAICEL-CYTEC Co., Ltd.) was used. The amount of hydrogen bond functional groups was 4.12·3 mol/g. [Synthesis Example m-6] Synthesis of a radical difunctional resin (A-7) A flask equipped with a thermometer, a cooling tube, and a stirring device was prepared. In this flask, 172 § bis bis, 1, hexa hexa y (made by Kanto Chemical Co., Ltd.), 148 g of glycidol (manufactured by Wako Pure Chemical Industries, Ltd.), and it was stirred for one hour under (10) seven times. mixing. Thereafter, ruthenium ruthenium 5 g - dibutyltin laurate was added to the reaction mixture, and the mixture was stirred at 8 ° C for 2 hours to cause a reaction. 200900816 ^ / yjii Next, 144 g of acrylic acid was added to the reaction mixture, and the mixture was reacted at % for 12 hours. The reaction mixture was subjected to infrared spectroscopy to eliminate the disappearance of the isocyanate-based absorption peak. After that, the reaction mixture is washed with ultrapure water, and the olefinic compound of 1,6-hexanediester diglycidyl ether of diisocyanate is obtained by the column _, I". By GPC, the synthesis of °, two lipids, the result is a family, and the molecular weight is complete. Since the =tree is intended to have two succinct and two amino decanoic acids in the molecule, the amount of the hydrogen bond functional group is calculated to be 8.7 〇 xl 〇 -3 m 〇 1 /g. Resin of the soil (1B) [Synthesis Example m-7] = Synthesis of a phenyl ether type partially-based epoxy resin A flask equipped with a thermometer, a cooling tube, and a mixing device was prepared. k bottle contains IGGg benzene_epoxy resin (Nippon Steel ^. mv Liu E, melting point is 84t), Q2g as ^A = stupid, ... 峨, A (four) g, G2 two = diethylamine, stir The solution is made into a uniform sentence, and the solution is made to burn == into the empty 耽'-face. This solution is won at 8 (rc for 2 hours, and then it is refluxed for one side, and the surface is allowed to react for 24 hours). After 3, the reaction mixture is refined, and then the super-injection is used to remove the sputum to obtain a thiolated partial acryl-methylation preparation. The number average molecule determined by the intracellular lung GPC?:树脂. The obtained resin is due to (iv) its peak is a single peak. The butyl group has 1 hydroxyl group, so the hydrogen bond functional group 200900816 27285ριί ί^ϋ·59χ] (Γ3 m°1/gn TM eucalyptus wax in the molecule % and oxy group, the amount of epoxy group is calculated to be 2 59 χ 1 3 [synthesis example m-8] I/g. Resin (10))························· Thermometer, cooling tube, stirring equipment ==6〇g double 酴·F type epoxy resin, -made by Dongdu Huacheng,) 36§Acrylic acid, 0.2§3—“. Next, - (4) burned the scented man to dry the side of the llGt for 5 hours, and the mixture was subjected to a core _: olefinic acid modified epoxy resin. After the obtained resin was prepared in a column, it was dissolved in toluene equivalent to the resin. After the benzene solution is washed, the toluene is injected; =% of the acrylylated epoxidized oxime is 曰. = The average molecular weight of the resin of the resin determined by Gpc is ~, wave material|peak. Since the obtained resin is in the molecule, the amount of the hydrogen bond functional group is calculated to be 2·6〇χ1 (Γ3 m〇i/g / in addition, the day 3 has one epoxy group in the molecule) The amount of epoxy groups was calculated to be 2.60 x 10 J m〇l/g. [Synthetic Example nr-9] ^ Moon 曰 (B 3). Synthesis of resorcinol diglycidyl squaring partial propylene fluorenated oxime resin = A flask equipped with a thermometer, a cooling unit, and a mixing device is provided.

, bottle, into 234 g resorcinol diglycidyl ether (Nagase ChemteX 95 200900816 company, Denacol ΕΧ_2 (Π, epoxy equivalent 117 _), 7 propylene l 5^Gg 甲笨, ig third butyl desert The chemical recording was carried out to obtain a uniform solution. The solution was stirred at 9 rc for 2 hours, and further refluxed while stirring for 6 hours. After the completion of the reaction, the reaction mixture was purified by a column. And washing with ultrapure water to obtain 5G% of the epoxy group-derived partially acrylylated epoxy resin. The obtained resin has a number average molecular weight of 294 as determined by Gpc. The peak is a single peak. Since the obtained resin has one hydroxyl group in the sub-group, the amount of the hydrogen bond functional group is calculated to be 3.4 〇 xi 〇 3 mol / g. Since the obtained resin has} ring in the molecule The amount of the epoxy group was calculated to be 3.40 x 10-3 m〇i/g. [Synthesis Example m-ίο] Synthesis of Resin (B-4) A flask equipped with a thermometer, a cooling tube, and a stirring device was prepared. The flask was charged with 296.2 g (2 moles) of phthalic anhydride and 1372 〇g (2 moles) of acrylic acid 2 -6-caprolactone adduct of hydroxyethyl ester (; placcelFA5, 分子量 molecular weight: 686 g/mo1, manufactured by Daicel Chemical Co., Ltd.), 4 g of ethylamine, 0.9 g of hydroquinone. This mixture is at 11 (^c) The reaction was carried out by stirring, and the reaction was carried out while monitoring the acid value. When the acid value reached 36 mgKOH/g, the reaction temperature was 90 ° C. Next, 680.82 g (2 mol) of bisphenol A condensate was added. Glycerol ether, 1.6 g of tetrabutylammonium bromide, heating and stirring until the acid value of the reaction mixture reached 2 mgKOH/g. After the reaction was completed, the reaction mixture was washed with ultrapure water and fed into the column 96 200900816 27285pif Order 'Available: a compound obtained by reacting a 6-hexane vinegar adduct of two dilute acid 2-silk vinegar with o-parabens, and reacting with the product * diglycidyl hydrazine. GPC called this resin for analysis, f its peak is a single peak, and the number average molecular weight is 116G. Since the obtained tree I day; ^ has a thiol group in the molecule, so the amount of the 氲 bond functional group is calculated, 8· 6χ1〇m〇l/g. Since the obtained resin has an epoxy group in the molecule, The amount of epoxy group was calculated to 8.6xl (T4 mol / g. F

[Synthesis Example m-ii] Synthesis of Resin (B-5) A flask equipped with a thermometer, a cooling tube, and a lining apparatus was prepared. In this case, the 19Q g benzene lacquer-type epoxy resin N_77〇 (made by Daisuke Mo), 500 mL of toluene, and the cake were added, and then the solution of 〇1 triphenylphosphine was added. When the nucleus was brought to a reflux state, the surface was stirred, and the surface was dropped with 35 g of acrylic acid in 2 hours. Thereafter, the mixture was stirred for a few hours to cause a reaction. After the reaction is completed, the reaction mixture is purified by a column and taken. The resin was obtained by washing. The resin was measured by *GPC, and the result was a single peak with a number average molecular weight of 1177. The oxygen equivalent was obtained by the measurement, and as a result, it was found that the epoxy group was changed to acrylic acid by f. The resin of the second soil has three radicals in the molecule, so the hydrogen bond functional group = 55xl 〇 -3 m〇1/g. Since the obtained resin exfoliated the epoxy group in the molecule, the number of epoxy groups was calculated to be 2.55 χ 1 〇 -3 m 〇 i / g. Three [Synthesis Example HM2; | Synthesis of Resin (B-6) 97 200900816, a thermometer, a cooling tube, and a lining device were prepared. In the flask, 172 g of diiso-hydrogen acid 1,6-hexane dihydrate (manufactured by Kanto Chemical Co., Ltd.) and 148 g of glycidol (manufactured by Wako Pure Chemical Industries, Ltd.) were placed, and the reaction was carried out by ribs for 1 hour. Then, 〇.05 g of dibutyltin dilaurate was added to the reaction mixture, and the mixture was stirred at 8 (rc for 2 hours). Next, 72 g of acrylic acid was added to the reaction mixture, and the mixture was stirred at 1 Torr: After several times of reaction, the reaction mixture was subjected to infrared spectroscopic analysis to confirm that the isocyanate-Wei peak disappeared. Then, the reaction mixture was washed with ultrapure water and purified by a column to obtain diisocyanate. 5 〇 醯 醯 醯 反应 反应 。 。 。 。 。 。 。 。 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此There are two urethane coordinating ligands and one hydroxyl group in the molecule, so the amount of the hydrogen bond functional group is calculated to be 7 73xl0-3. The obtained resin has one epoxy group in the molecule, so the bad emulsion group 1 nasal output is 2.58xl〇-3mol/g. (1C) Shuyuezhi (CM): Neighboring lacquer-type solid ring separated by column: ^EOCN_102(): manufactured by Nippon Kayaku Co., Ltd. The softening point measured by the method is 75t and the epoxy equivalent is 215 g/eq.

Because the resin has an oxygen equivalent weight of 215 g/eq, the resin (C-based molecular weight is 215. Therefore, the resin (tetra)oxy_1/g. Since the resin does not contain a hydrogen bond functional group, the oxygen bond function The basis weight is G. In addition, the 98 200900816 272S5pif weight of the resin was measured by GPC, and the average molecular weight 'result was 1075 〇, and the resin (C~2): bisphenol a type epoxy resin (Epikote 1003: JER manufacturing 'borrowed' The softening point measured by the ring and ball method was 89 ° C, and the epoxy equivalent was 720 g / eq. Since the resin had two epoxy groups in the molecule, the molecule 1 of the resin was calculated to be 1440. The amount of the oxygen was calculated to be 139 χ 1 〇 -3 mol / g. Since the resin hardly has a molecular weight distribution, the weight average is also 1440. Further, the resin is represented by the following structural formula, and each repeating unit (molecular weight is 284.4) has one hydroxyl group. Since the molecular weight of this resin is 1440, n is calculated to be 3.87. Therefore, the average molecular weight per molecule is 3.87 hydroxyl groups, so the amount of the oxime bond functional group is calculated to be 2 69 χ 1 (Γ3 mol/g 〇

In the above formula, the number indicates the molecular weight. Epoxy Resin (C-3) (Comparative) Bisphenol A type epoxy wax (Epik〇te 828EL: manufactured by JER, epoxy equivalent i90g/eq) Since this resin (C-3) has 2 in the molecule Since the molecular weight of the resin is calculated to be 380. Therefore, the cross-linking amount of the resin is 5.26XHT3 m〇i/g. In addition, the resin is also represented by the formula (2). η was calculated to be 0.14. Therefore, since the resin (C-3) had 〇14° _ groups, the amount of hydrogen bond functional groups was calculated to be 3.7 χ10·4 mol/g. Since this tree ^ 99 200900816 2 / 2 in the chamber The temperature is liquid, so the softening point is less than 4 〇 ° C. [Evaluation method], ', the evaluation methods of Examples (6) to 6 and Comparative Examples HM to 4 are explained. Here, 'Measurement 〇> The bubble resistance of the night crystal sealant, U) = coatability of the sealant, Ui) seal appearance and adhesion strength, and iv) the viscosity of the sealant on the day of the liquid were evaluated for the characteristics of the liquid crystal sealant. Each evaluation The details of the measurement method are as follows. f 耐 Liquid Crystal Sealant Leakage Resistance A liquid crystal sealing agent to which a spacer was added was prepared by adding 1 part of a 4.8 // m spherical spacer to the liquid crystal sealing agent prepared by the following method. Next, a 4 mm mmx45 glass substrate (RT-DM88PIN: manufactured by EHC Corporation) with a transparent electrode and an alignment film was prepared. Then, the above composition was filled into a square seal pattern of 35 mm x 40 mm (a cross-sectional area of 3,500 ym 2 ) on the upper edge of the glass substrate as a container (manufactured by Hitachi Plant Technologies). Using a dispenser (manufactured by Hitachi Plant Technologies Co., Ltd.), a liquid crystal material (MLC-11900-000: manufactured by Merck Co., Ltd.) having the same amount of panel content as the bonded panel was precisely dropped into the sealing pattern of the substrate. The glass device was laminated on the glass substrate and the opposite glass substrate under a reduced pressure of 10 Pa. Next, the above-mentioned overlapped glass was sandwiched between two 40 mm x 45 mm glass substrates prepared in advance. The substrate is fixed by applying a load. The glass substrate is subjected to Chromium Sputtering on both sides thereof. Next, 100 200900816 27285pif restores the overlapped glass substrate to atmospheric pressure and heats it under l2〇r It is hardened by a few minutes (hereinafter, it is called "hardening process in a leak-proof test"). The linearity of the sealing pattern of the liquid-crystal display panel which is an index of leak-proof property, and the sealing linearity is evaluated by the following method. [The ratio of the maximum width to the minimum width of the seal]% = [Minimum width of the seal] / [Maximum width of the seal] χ 1 〇〇 The above ratio is large 95% or more: ◎ (excellent) (The above ratio is 80% or more and less than 95%: 〇 (slightly superior) The above ratio is less than 80%: X (poor) ' ii) The coating property of the liquid crystal sealing agent is The liquid crystal sealing agent used in the above i) was filled into a syringe under vacuum. Next, the injection cryo-filled with a needle having a diameter of 0.4 mm was placed on a dispenser (manufactured by Hitachi Plant Technologies), and then a glass substrate for a liquid crystal display panel of 300 mm x 400 mm (manufactured by Nippon Electric Glass Co., Ltd.) was used. ) Draw 50 35 mm x Q 40 mm seal patterns. At this time, the discharge pressure was set to 〇·3 MPa, the cross-sectional area was set to 3500 //m2, and the coating speed was set to 100 mm/sec. The seal shape of the drawn seal pattern was evaluated according to the following criteria. The frame shape of the seal is not broken at all, and the shape of the seal is 48 to 5 〇彳. ◎ (excellent) The above frame shape is 45 or more and less than 48: 〇 (slightly sorrowful) 101 200900816 Less than 44 shapes: χ (poor)

Ul) Seal appearance and adhesion strength Using a screen, a liquid crystal sealant prepared in a 25 mm x 45 mm x thickness 4 mm non-glass, C 1 ) was coated into an I open " sealing pattern with a diameter of 1 mm. Next, the alkali-free glass and the pair of the same glass were fixed in a ten-shape and fixed, and the fixed pair of glasses were heated at 120 C for 60 minutes to be bonded (hereinafter referred to as " Then, in the test (the hardening step), the obtained two glass plates (hereinafter referred to as "the test piece were stored in a thermostat at a humidity of 5〇% for 24 hours, and then visually observed. The appearance of the seal can also be used as a standard for liquid crystal contamination of liquid crystal sealants. The appearance of the seal is evaluated according to the following criteria. No gaps or outflows were observed by visual inspection: ◎ (excellent) Small voids or outflows were visually observed: △ (slightly poor Visually visible outflows and voids: χ (Poor) Bait/Material's use of a tensile tester (manufactured by Intesc〇) to determine the tensile strength of the test piece taken from the constant temperature bath using the tensile speed of the God I 7 knife. The strength is then evaluated according to the following criteria: Then the intensity is greater than or equal to 10Mpa: ◎ (excellent) Then the strength is greater than or equal to 7 Mpa and less than 1〇jyjpa. 〇)) Then the strength is less than 7MPa less than: χ (poor) iv) Sealant Degree measurement 102 200900816 27285pif The viscosity of the composition is E-type rotary viscose (manufactured by BROOKFIELD: digital rheometer, model: ten ULTRA) and cp_52 cone 311 type with a radius of 2 mm and an angle of 3. The measurement was carried out under the following conditions at a rotation speed of 1, 〇jpm = viscosity at 25 ° C: The liquid crystal sealing agent of the present invention was measured at 25 minutes after it was set for 5 minutes.

Viscosity at 80 C: The liquid crystal sealing agent of the present invention was placed in a cup of a giant 4 rotational viscometer to be 5. (The temperature rise rate of :/min is raised to 8 〇ΐ: 垔80° C. and left for 5 minutes, and then measured. 'In this case', the liquid crystal sealant exceeds the measurement limit at 8 degrees and cannot be measured. In the case of the parallel method (RheoSt surface RS150: manufactured by HAAKE), the measurement by the plate method is based on the standard method of the above-mentioned model, and the temperature is raised to the thief at 5t/eight^= degrees, and the gorge is immediately performed. It is a CP-52 type cone-and-plate type sensor with E-type rotary type material (digital flow rheometer, Wei.^ ULTRA, manufactured by Brain 0K Service D) and radius ^3, angle 3 The measurement was carried out at a rotation speed of 〇5 and 5.0 rpm, and the value of [viscosity at 25, ^·卬111] / [viscosity at 25 ° C, 5.0 φηη] was expressed as follows: rpm Example mi] ^ ° 30 parts of resin ((A-3), 30 parts of resin (A-5), 10 parts of ring most) prepared as a curable resin, with 1 part of hot radical polymerization Starting agent i, 8 , 曰: 1, 20 parts filled ^ 18 parts of epoxy hardener 1. These were premixed with a mixer of 2009 200900816. Next, a mixture of three rolls was used. The kneading was carried out until the solid raw material reached 4 # m. Then, the mixture was filtered with a mesh pore size of 10 (MSP-10-E10S: manufactured by ADVANTEC) to perform vacuum defoaming. The liquid crystal sealing agent is obtained by the treatment. The amount of the hydrogen bond functional group in the curable resin contained in the liquid crystal sealing agent is 3.55 x l 〇 3 mol / g ' The amount of the epoxy group is 〇 47 x 1 〇 -3 m 〇 1 / g The viscosity of the liquid crystal sealant thus obtained at 25 is 440 Pa s at 5 rpm and mo pa. s at 1 rpm, 280 Pa.s at 5 rpm.

Since the viscosity measured by the E-type rotary viscometer at 80 ° C was more than 780 Pa·s, it was measured by the parallel plate method (Can (3) Hall RS15 〇: manufactured by HAAKE). The result is 9 〇〇E + 〇5 pa.s. The thixotropy index was 1.6 °. The liquid crystal sealant was evaluated by various tests. [Examples - 2 to 6] The respective components shown in the following Table 5 were prepared, and a liquid 4 sealant was prepared in the same manner as in the examples. Each liquid crystal sealing agent was evaluated in the same manner as in Example guan-1. [Comparative Example Melon-1] The components shown in Table 2 were prepared and prepared in the same manner as in the example. For each liquid crystal seal, the same method as the example melon_1 is the same. The "hardening step in the evaluation of the resistance to vapor leakage" is performed by irradiating 3 ultraviolet rays 104 before heating at 120 C for 60 minutes. 200900816 27285pif And proceed. Further, "the hardening step in the subsequent test" was also carried out by irradiating ultraviolet rays of 3,000 mJ before heating at 120 °C for 60 minutes. [Comparative Example 、-2, 3] Each component shown in the following Table 6 was prepared, and a liquid crystal sealing agent was prepared in the same manner as in Example ΠΤ-1. The same evaluation as in Example ΠΙ-1 was carried out for each liquid crystal sealing agent. [Comparative Example - 4] Each component shown in the following Table 6 was prepared, and a liquid crystal sealing agent was prepared in the same manner as in Comparative Example. The same evaluation as in Example ΠΤ-1 was carried out for each liquid crystal sealing agent. 105 200900816 [Table 5]

Hydrogen bond functional group amount (xlO - 3 mol / g) Ring + base amount (X 10 'J mol / g) Example Μ -1 Example m - 2 Example dish - Example ΙΠ -4 Example ΙΠ - 5 EXAMPLES -6 COMPOSITION (1A) Resin A-1 4.38 0.00 30 — — — — — A-2 3.90 0.00 — — — 10 — A-3 5.46 0.00 30 20 — — 70 20 A-4 4.36 0.00 — 25 — — — 25 A-5 1.99 0.00 30 25 — 20 — 25 A-6 4.12 0.00 一 — — — 15 — (1B) Resin B-1 2.59 2.59 — 25 30 I— 25 B-2 2.60 2.60 — — - — — B-3 3.40 3.40 — — 25 40 — — B-4 0.86 0.86 - — 30 40 — — (1C) Resin C-1 0.00 4.65 10 5 15 — 5 — C-2 2.69 1.39 — — — — — 5 Filler - 20 25 10 15 10 25 4 - — — — 10 15 — — Thermal Radical Polymerization Starter — — 1 1 1 2 1 1 Epoxy Hardener — — 8 8 3 5 8 8 Thermoplastic Polymer — — — 2 — — — 2 The amount of hydrogen bond functional groups in the resin (Xl〇_3mol/g) 3.55 2.24 1.89 2.10 4.83 3.33 The amount of epoxy groups in the resin (xl〇_3inol/g) 0.47 0.23 2.58 1.70 0.23 0.65 viscosity 25 °C/0.5 rpm (Pa*s) 440 480 320 180 190 450 25°C/l.〇rpm (Pa-s) 350 310 210 80 180 280 25〇C/5.0 rpm (Pa-s) 280 260 180 40 170 220 80°C/l.〇rpm (Pa-s) Measurement limit measurement limit measurement limit measurement limit measurement limit The viscosity at 80 °C measured by the parallel plate method (xlO^a·s) 9 9 9 9 9 9 Thixotropic index 1.6 1.8 1.8 4.5 1.1 2.0 Evaluation (i) Leakage resistance ◎ ◎ ◎ ◎ ◎ ◎ (ii) Coating property ◎ ◎ ◎ ◎ ◎ ◎ (iii) Subsequent strength ◎ ◎ ◎ ◎ ◎ ◎ (iv) Viscosity stability ◎ ◎ ◎ ◎ ◎ ◎ 106 200900816 Ζ /Ζΰ^ρΐΙ

[Table 6]

Hydrogen bond functional group amount (xlO'3 mol/g) Epoxy group amount Cxicr3 mol/g) Comparative Example ΙΠ-1 Comparative Example ffi-2 Comparative Example ΠΙ-3 Comparative Example ΙΠ-4 (1A) Resin A-6 4.12 0.00 — — 66.7 60 A-7 8.70 0.00 30 30 33.3 — (1B) Resin B-5 2.55 2.55 30 - — A B-6 7·73 2.58 40 70 — — (1C) Resin C-1 0.00 4.65 5 — — — C-3 0.37 5.26 - - - 40 1 — — 20 55 — — Filler 2 — — — — — 10 Composition 3 — — — — 25 — Thermal radical polymerization from 1 — — — 3.5 — — initiator 4 — — — — 1,7 — Epoxy hardener 2 — — — — 16.7 10 3 — — 25 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — Photoradical polymerization initiator - 1 - 2 The amount of hydrogen bond functional groups in the resin (xl (Tmol / g) 6.16 8.02 11.29 2.62 The amount of epoxy groups in the resin (x = 0_3mol / g) 1.93 1.81 0.00 2.10 25〇C/0.5 rpm (Pa*s) 260 1320 360 255 25°C/l.〇rpm (Pa's) 250 510 340 250 25X75.0rpm (Pa.s) 240 260 320 243 Viscosity 80°C/1.0rpm ( Pa-s) 350 Limit 380 270 Viscosity at 80 °C measured by the parallel plate method (Pa-s) 8.00Ε+ 02 9.00E+ 05 9.00E+ 02 6.00E+ 02 Thixotropic index 1.1 5.3 1.1 1.0 (i) Leakage resistance X 〇 XX evaluation (ii) coatability 〇 X 〇〇 price (iii) subsequent strength Δ X Δ X (iv) viscosity stability Δ XXX by Examples II-1 to 6 and Comparative Example 1 Π -1 to 4 In comparison, it is understood that the liquid crystal sealing agent of the present invention containing a curable resin having a hydrogen bond functional group amount and an epoxy group content within a specific range is excellent in leakage resistance, adhesion, and coating property. Comparing with Comparative Example m-4, it is known that the liquid crystal _ sealant of the present invention contains softening 07 07 200900816, ====== resistance to dioxygen crystal [industrial availability] force rail liquid crystal sealing The curable resin composition can be quickly and sufficiently cured by simply using m '. So make

The liquid crystal sealing agent produced by using the liquid crystal dense curable resin composition of the present invention has high curability and is excellent in line leakage resistance, and can suppress liquid crystal contamination, so that it can effectively provide display characteristics. Liquid crystal sealing agent for liquid crystal display panel. This application is based on 1) Application No. JP2007-039938, filed on February 20, 2007, 2) Application No. JP2007-169749, filed on June 27, 2007, 3) Application filed on November 14, 2007 Apply for the compilation of Tiger JP2007-295925 and claim priority. The contents disclosed in the above specification are all incorporated in the specification of the present application. θ [Simple description of the diagram] None [Description of main component symbols] None

Claims (1)

200900816 X. Patent application scope: It contains: 1 · a kind of curable resin composition for liquid crystal sealing, acrylic resin; and / or (meth) propyl _ modified epoxy resin, which is above or above tamping Epoxy and (meth) propylene-based; - a thermal radical polymerization initiator; and filler, The viscosity of the sclerosing tree tester for liquid crystal sealing measured at 25 C, 1. rpm is 5 〇pa s~5 〇〇pa s, and at 80 C, 1.0 rpm. The viscosity below is greater than 5〇〇pa.s. The curable resin composition for liquid crystal sealing according to the above-mentioned patent application, wherein the average primary particle diameter of the filler is equal to or less than $4, and the specific surface area is i m2/g~· M2/g, and the content of the filler is 1 part by weight to 1 part by weight based on the total amount of the acrylic resin and the (meth)acrylic modified epoxy resin, and is [by type E viscosity meter] The measured thixotropic index defined by the viscosity at 25 ° C, 0.5 rpm] / [viscosity at 25 〇 c, 5 〇 ri) measured by an E-type viscosity meter was 丨丨 ～ 5.0. 109 1 . The sclerosing composition for liquid crystal sealing according to claim 7 or 2, wherein the towel is subjected to the thermal radical 3 polyf starting agent at a predetermined temperature. The thermal radical polymerization starts at 4 hours in the thermal decomposition reaction; the temperature at which the temperature is reduced to half is defined by the temperature of the first half of the thermal radical polymerization, and the 10-hour half-life temperature is 40. (: 〜8 (TC. 6) 4. A curable resin composition for liquid crystal sealing, comprising: a radical having a carbon-carbon double bond capable of radical polymerization in 171 molecules; 200900816 _ - j hardening resin; The heat-radical-polymerization initiator; the radical-chain-transfering agent; and the filler of the liquid crystal sealing agent according to the fourth aspect of the invention, wherein the radical chain transfer agent is sulfur Alcohol. ί 6. The curable resin composition for liquid crystal sealing according to Item 4 or 5, wherein the thiol as the radical chain transfer agent is a secondary thiol having a number average molecular weight of 400 to 2,000. class. 7. The curable resin composition for liquid crystal sealing according to claim 4, wherein the curable resin composition for liquid crystal sealing is 25 measured by a Ε-type viscosity meter. The viscosity at 〇 1.0 ipm is 50 Pa.s~5〇〇 Pa.S ' and the viscosity at 80 ° C, 1.0 rpm is greater than 500 Pa.s. A curable resin composition for liquid crystal sealing comprising: $ " a resin composition having a carbon-carbon double bond capable of radical polymerization, a hydrogen bond functional group, and an epoxy group; And a filler, wherein the resin composition comprises two or more resins selected from the group consisting of: (1A) free red neon, and two carbons from the t-based polymerization of the ruthenium molecule - Carbon double bond, and the above gas key Lu Yue b base! 1.5ΧΚΓ3 m〇l/g~6.〇χ1〇-3 m〇1/g ; 〇B) free radical anti-ship resin' has a nitrogen bond in the ruthenium molecule 110 200900816 27285pif can be based on an epoxy group, And a carbon-carbon double bond capable of undergoing radical polymerization, and the above-mentioned hydrogen bond functional group amount is 1.00xG-Vol/g~5.GxlG.3mol/g; and a mouth, jic) epoxy resin, which is in the ruthenium molecule An epoxy group having no carbon-carbon double bond capable of undergoing radical polymerization, and having a softening point of 40 ° C or more as measured by a ring and ball method, and a weight average molecular weight of 5 〇〇 5 _ 5 _; The amount of the hydrogen bond functional group in the material is 10 x 10 -4 mol to 6. Ox Hr3 mol / g; the amount of the epoxy group in the above resin composition is 1 〇χ 1 〇 · 4 2 6 χ l (T3 mol / g. B t 9 · as stated The sclerosing resin for liquid crystal sealing according to the eighth aspect of the invention, wherein the hydrogen bond functional group of the composition towel is a light base. 10. According to the scope of claim 8 The curable resin for liquid crystal sealing, the composition of the above-mentioned (1 Α) radical reactive resin is a resin represented by the following formula (al) or formula (a2); [In the above formula (al), the formula (), R2, R3, and R4 represent a hydrogen atom or a methyl group in a touch; J is a hydrogen atom, a pyridyl group of Wei, and a number of 1 to 4; _ silk or alkoxy having a carbon number of 1 to 4; η represents an integer of 1 to 4; 1 represents an integer of 1 to 4; 111 200900816 A. I y li A is -CH2-, _C(CH3)2- , an organic group represented by -S02-, or -O-]; (General formula (a2) [in the above formula (a2), R5, R6, R7 and Rs each independently represent a hydrogen atom or a fluorenyl group; Rq independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an allyl group, a hydroxyalkyl group having 1 to 4 carbon atoms or An alkoxy group having a carbon number of 1 to 4; r represents an integer of 1 to 4; and p represents an integer of 1 to 4]. The curable resin composition for liquid crystal sealing according to claim 8, wherein the (1Α) radical reactive resin is represented by the following formula (a3) or formula (a4). Resin In the above formula (a3), R! and R2 each independently represent a ruthenium atom or a methyl group; and Rm* independently represents a ruthenium atom, an alkyl group having 1 to 4 carbon atoms, and an ene 112 200900816 27285pif propyl, a calcined group having a carbon number of 1 to 4 or an alkoxy group having a carbon number of 1 to 4; η represents an integer of 1 to 4, and Α is CH2-, -C(CH3)2-, - An organic group represented by S02-, or -0-]; General formula (a4) [In the above formula (a4), R5 and R6 each independently represent a hydrogen atom or a fluorenyl group]. 12. The curable resin composition for liquid crystal sealing according to claim 8, wherein the curable resin composition for liquid crystal sealing is measured at a temperature of 25 ° C and 1.0 i * pm as measured by a £-type viscosity meter. The viscosity is 50 Pa.s~500Pa.s and is 80. The viscosity of the liquid crystal sealing curable resin composition as described in claim 8, wherein the curable resin composition for liquid crystal sealing further contains a radical. The curable resin composition for liquid crystal sealing according to claim 13, wherein the curable resin composition for liquid crystal sealing is measured at 25 ° C and 1.0 rpm by an E-type viscosity meter. The viscosity is 50 Pa. s~ 500 Pa.s, and the viscosity at 80 ° C, 1.0 rpm is greater than 500 Pa.s. 15. A method for manufacturing a liquid crystal display panel, which is hardened by liquid crystal sealing. The resin composition is bonded to two substrates to form a liquid crystal display panel, and includes: 113 200900816 A step of preparing a first substrate, wherein the first substrate includes a domain, and the frame-shaped display region is as claimed In the above-mentioned display area of the patent range 〗 〖, the wide shoulder and the eighth item, the liquid crystal densely pours into the area, and the shape of the liquid is in the above-mentioned display area of the Si: state or on the other-side plate; = the first substrate, and the opposite Step of superposing the second substrate. H is a step of hardening the liquid crystal sealing resin composition by heating (J 114 200900816 27285pif VII. Designated representative drawing: (1) The representative drawing of the case is: None. (2) The representative A brief description of the symbol of the figure: None. 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: General formula (al )