JP6127223B1 - Photocurable resin composition, display element sealant, liquid crystal sealant, liquid crystal display panel, and method for producing liquid crystal display panel - Google Patents

Abstract

An object of the present invention is to provide a photocurable resin composition having high curability for visible light and capable of highly suppressing liquid crystal contamination when used as, for example, a liquid crystal sealant. The photocurable resin composition of the present invention has a curable compound A having an ethylenically unsaturated double bond in the molecule, an anthraquinone skeleton or thioxanthone skeleton in the molecule, and one or more NHCO groups. And a compound B having an NHCO group equivalent represented by (I) of 350 g / eq or less. NHCO group equivalent (g / eq) = molecular weight / number of NHCO groups contained in one molecule: Formula (I)

Description

  The present invention relates to a photocurable resin composition, a display element sealant, a liquid crystal sealant, a liquid crystal display panel, and a method for producing a liquid crystal display panel.

  In recent years, display panels such as liquid crystal and organic EL have been widely used as image display panels for various electronic devices such as mobile phones and personal computers. For example, a liquid crystal display panel includes two transparent substrates having electrodes provided on the surface, a frame-shaped sealing member sandwiched between them, and a liquid crystal material sealed in a region surrounded by the sealing member And have.

  The liquid crystal display panel can be manufactured by, for example, a liquid crystal dropping method. Production of a liquid crystal display panel by a liquid crystal dropping method is as follows: (1) A liquid crystal sealing agent is applied to the inner edge of a transparent substrate to form a frame for filling with liquid crystal; (2) Liquid crystal is dropped into the frame; (3) After superposing two substrates under high vacuum while the liquid crystal sealant is in an uncured state, (4) curing the liquid crystal sealant.

  Thus, in the liquid crystal dropping method, photocuring or thermosetting is performed in a state where the uncured liquid crystal sealant and the liquid crystal material are in contact with each other. Therefore, the liquid crystal sealant is required not only to have high curability but also to reduce contamination of the liquid crystal material.

  As a liquid crystal sealant used in the liquid crystal dropping method, a photocurable resin composition containing a compound having a (meth) acryloyl group in the molecule and an anthraquinone derivative as a photopolymerization initiator has been proposed (for example, Patent Document 1). ). There has also been proposed a photocurable resin composition comprising a photopolymerizable oligomer, a compound B obtained by reacting hydroxythioxanthone as a photopolymerization initiator with a compound having two or more epoxy groups in the molecule. (For example, patent document 2). Furthermore, a sealing agent for liquid crystal display elements has been proposed that includes a curable resin and a compound obtained by reacting an oxime ester and a polyfunctional isocyanate as a photopolymerization initiator (for example, Patent Document 3).

International Publication No. 2007/074782 International Publication No. 2012/0777720 JP 2014-98763 A

  However, since the composition shown in Patent Document 3 contains a photopolymerization initiator having low light absorption in the visible light region, the curability to light in the visible light region is low. Since the compositions shown in Patent Documents 1 and 2 contain a photopolymerization initiator having an anthraquinone skeleton or a thioxanthone skeleton, the curability to light in the visible light region is good. There is a demand for further reduction of elution. Thus, it is desired to provide a photocurable resin composition that has high curability with respect to light in the visible light region and can highly suppress liquid crystal contamination.

  The present invention has been made in view of the above problems. For example, when used as a display element sealant, particularly as a liquid crystal sealant, the photocurability is high in visible light curing and can highly suppress liquid crystal contamination. It aims at providing a resin composition.

（式（４）及び（５）において、Ｌ_１は、それぞれ独立に単結合、炭素数１〜１０のアルキレン基、炭素数１〜１０のアルキレンオキシ基、炭素数１〜１０のアルキレンチオ基、炭素数６〜１０のアリーレン基、炭素数６〜１０のアリーレンオキシ基又は炭素数６〜１０のアリーレンチオ基を表し、Ｘは、分子内に少なくともｐ個のイソシアネート基を有する化合物から誘導される有機基を表し、ｐは、１〜５の整数を表す）
［５］ 前記化合物Ｂが、分子内にエチレン性不飽和二重結合をさらに有し、且つ前記硬化性化合物Ａが、アントラキノン骨格又はチオキサントン骨格を有しない、［１］〜［４］のいずれかに記載の光硬化性樹脂組成物。
［６］ 前記化合物Ｂの含有量が、前記硬化性化合物Ａに対して０．０１〜１０質量％である、［１］〜［５］のいずれかに記載の光硬化性樹脂組成物。
［７］ 前記硬化性化合物Ａが、分子内にエポキシ基をさらに有する、［１］〜［６］のいずれかに記載の光硬化性樹脂組成物。
［８］ 分子内にエポキシ基を有する熱硬化性化合物Ｃと、熱硬化剤Ｄとをさらに含み、且つ前記熱硬化性化合物Ｃは、前記硬化性化合物Ａとは異なる、［１］〜［７］のいずれかに記載の光硬化性樹脂組成物。
［９］ 前記熱硬化剤Ｄが、ジヒドラジド系熱潜在性硬化剤、イミダゾール系熱潜在性硬化剤、アミンアダクト系熱潜在性硬化剤、及びポリアミン系熱潜在性硬化剤からなる群より選ばれる１以上である、［８］に記載の光硬化性樹脂組成物。
［１０］ ［１］〜［９］のいずれかに記載の光硬化性樹脂組成物からなる、表示素子シール剤。
［１１］ ［１］〜［９］のいずれかに記載の光硬化性樹脂組成物からなる、液晶シール剤。
［１２］ 液晶滴下工法用の液晶シール剤である、［１１］に記載の液晶シール剤。
［１３］ ［１１］又は［１２］に記載の液晶シール剤を用いて、一方の基板にシールパターンを形成する工程と、前記シールパターンが未硬化の状態において、前記シールパターンの領域内、又は前記一方の基板と対になる他方の基板に液晶を滴下する工程と、前記一方の基板と前記他方の基板とを、前記シールパターンを介して重ね合わせる工程と、前記シールパターンを硬化させる工程と、を含む、液晶表示パネルの製造方法。
［１４］ 前記シールパターンを硬化させる工程は、前記シールパターンに光を照射して前記シールパターンを硬化させる工程を含む、［１３］に記載の液晶表示パネルの製造方法。
［１５］ 前記シールパターンに照射する光は、可視光領域の光を含む、［１４］に記載の液晶表示パネルの製造方法。
［１６］ 前記シールパターンを硬化させる工程は、光が照射された前記シールパターンを加熱して硬化させる工程をさらに含む、［１４］又は［１５］に記載の液晶表示パネルの製造方法。
［１７］ 一対の基板と、前記一対の基板の間に配置された枠状のシール部材と、前記一対の基板の間の前記シール部材で囲まれた空間に充填された液晶層とを含み、前記シール部材が、［１１］又は［１２］に記載の液晶シール剤の硬化物である、液晶表示パネル。[1] A curable compound A having an ethylenically unsaturated double bond in the molecule, an anthraquinone skeleton or thioxanthone skeleton in the molecule, and an NHCO group, and an NHCO group equivalent represented by the formula (I) is The photocurable resin composition containing the compound B which is 350 g / eq or less.
NHCO group equivalent (g / eq) = molecular weight / number of NHCO groups contained in one molecule: Formula (I)
[2] The photocurable resin composition according to [1], wherein the compound B has 3 or more NHCO groups in the molecule.
[3] The photocurable resin composition according to [1] or [2], wherein the compound B has a burette skeleton or an allophanate skeleton in the molecule.
[4] The photocurable resin composition according to any one of [1] to [3], wherein the compound B is represented by the following formula (4) or formula (5).

(In Formulas (4) and (5), L ₁ is each independently a single bond, an alkylene group having 1 to 10 carbon atoms, an alkyleneoxy group having 1 to 10 carbon atoms, an alkylenethio group having 1 to 10 carbon atoms, Represents an arylene group having 6 to 10 carbon atoms, an aryleneoxy group having 6 to 10 carbon atoms, or an arylenethio group having 6 to 10 carbon atoms, and X is derived from a compound having at least p isocyanate groups in the molecule. Represents an organic group, and p represents an integer of 1 to 5)
[5] Any of [1] to [4], wherein the compound B further has an ethylenically unsaturated double bond in the molecule, and the curable compound A does not have an anthraquinone skeleton or a thioxanthone skeleton. The photocurable resin composition described in 1.
[6] The photocurable resin composition according to any one of [1] to [5], wherein the content of the compound B is 0.01 to 10% by mass with respect to the curable compound A.
[7] The photocurable resin composition according to any one of [1] to [6], wherein the curable compound A further has an epoxy group in the molecule.
[8] A thermosetting compound C having an epoxy group in the molecule and a thermosetting agent D, and the thermosetting compound C is different from the curable compound A, [1] to [7 ] The photocurable resin composition in any one of.
[9] The thermosetting agent D is selected from the group consisting of a dihydrazide thermal latent curing agent, an imidazole thermal latent curing agent, an amine adduct thermal latent curing agent, and a polyamine thermal latent curing agent. The photocurable resin composition according to [8], which is as described above.
[10] A display element sealing agent comprising the photocurable resin composition according to any one of [1] to [9].
[11] A liquid crystal sealant comprising the photocurable resin composition according to any one of [1] to [9].
[12] The liquid crystal sealant according to [11], which is a liquid crystal sealant for a liquid crystal dropping method.
[13] In the step of forming a seal pattern on one substrate using the liquid crystal sealant according to [11] or [12], and in the state of the seal pattern in an uncured state, or Dropping the liquid crystal on the other substrate paired with the one substrate, superimposing the one substrate and the other substrate through the seal pattern, and curing the seal pattern; A method for manufacturing a liquid crystal display panel.
[14] The method for manufacturing a liquid crystal display panel according to [13], wherein the step of curing the seal pattern includes a step of irradiating the seal pattern with light to cure the seal pattern.
[15] The method for manufacturing a liquid crystal display panel according to [14], wherein the light applied to the seal pattern includes light in a visible light region.
[16] The method for manufacturing a liquid crystal display panel according to [14] or [15], wherein the step of curing the seal pattern further includes a step of heating and curing the seal pattern irradiated with light.
[17] including a pair of substrates, a frame-shaped sealing member disposed between the pair of substrates, and a liquid crystal layer filled in a space surrounded by the sealing member between the pair of substrates, A liquid crystal display panel, wherein the seal member is a cured product of the liquid crystal sealant according to [11] or [12].

  According to the present invention, for example, when used as a display element sealant, particularly a liquid crystal sealant, it is an object to provide a photocurable resin composition that has high curability to visible light and can highly suppress liquid crystal contamination. And

1. Photocurable resin composition The photocurable resin composition of this invention contains the curable compound A and the compound B, and may further contain the thermosetting compound C and the thermosetting agent D as needed.

1-1. Curable compound A
The curable compound A contained in the photocurable resin composition of the present invention is a compound having an ethylenically unsaturated double bond in the molecule. The compound having an ethylenically unsaturated double bond in the molecule is preferably a compound having a (meth) acryloyl group in the molecule. The number of (meth) acryloyl groups per molecule is 1 or 2 or more. The compound having a (meth) acryloyl group in the molecule may be a monomer, an oligomer or a polymer. (Meth) acryloyl group means acryloyl group or methacryloyl group, and (meth) acrylate means acrylate or methacrylate. However, the curable compound A does not have an anthraquinone skeleton or a thioxanthone skeleton.

  Examples of compounds having one (meth) acryloyl group in one molecule include (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid 2-hydroxyethyl ester. Alkyl esters are included.

  Examples of compounds having two or more (meth) acryloyl groups in one molecule include di (meth) acrylates such as polyethylene glycol, propylene glycol, and polypropylene glycol; di (meth) tris (2-hydroxyethyl) isocyanurate Acrylate; Di (meth) acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol; Diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A Di (meth) acrylate of triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane; diol or tri (meth) acrylate of triol; Di (meth) acrylate of a diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate; trimethylolpropane tri (meth) acrylate, or Pentaerythritol tri (meth) acrylate or oligomer thereof; poly (meth) acrylate of dipentaerythritol; tris (acryloxyethyl) isocyanurate; caprolactone-modified tris (acryloxyethyl) isocyanurate; caprolactone-modified tris (methacryloxyethyl) ) Isocyanurate; polyacrylate or polymethacrylate of alkyl-modified dipentaerythritol; polyacrylate of caprolactone-modified dipentaerythritol Hydroxypivalate neopentyl glycol diacrylate or dimethacrylate; caprolactone-modified hydroxypivalate neopentyl glycol di (meth) acrylate; ethylene oxide-modified phosphate acrylate or dimethacrylate; ethylene oxide-modified alkylated phosphate (meta ) Acrylate; neopentyl glycol, trimethylolpropane, pentaerythritol oligo (meth) acrylate and the like.

  The curable compound A may further have an epoxy group in the molecule. The number of epoxy groups per molecule is 1 or 2 or more. If the curable compound A further has not only a (meth) acryloyl group but also an epoxy group in the molecule, the photocurable resin composition containing it can be imparted with photocurability and thermosetting properties. Thereby, the sclerosis | hardenability of hardened | cured material can be improved.

  The compound having a (meth) acryloyl group and an epoxy group in the molecule can be, for example, a (meth) acrylic acid glycidyl ester obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst. .

  The epoxy compound to be reacted may be a polyfunctional epoxy compound having two or more epoxy groups in the molecule, and suppresses the decrease in the adhesiveness of the cured product of the photocurable resin composition due to excessive increase in the crosslinking density. In view of this, a bifunctional epoxy compound is preferable. Examples of bifunctional epoxy compounds include bisphenol type epoxy compounds (bisphenol A type, bisphenol F type, 2,2′-diallyl bisphenol A type, bisphenol AD type, hydrogenated bisphenol type, etc.), biphenyl type epoxy compounds, And naphthalene type epoxy compounds. Of these, bisphenol A type and bisphenol F type bisphenol type epoxy compounds are preferred from the viewpoint of good coating properties. The bisphenol type epoxy compound has advantages such as excellent coating properties as compared with the biphenyl ether type epoxy compound.

  The compound having a (meth) acryloyl group and an epoxy group in the molecule may be one kind or a combination of two or more kinds.

  You may combine the compound A1 which has a (meth) acryloyl group in a molecule | numerator, and does not have an epoxy group, and the compound A2 which has a (meth) acryloyl group and an epoxy group in a molecule | numerator. Thereby, when the photocurable resin composition further contains an epoxy compound as the thermosetting compound C, the epoxy compound, and a compound A1 having a (meth) acryloyl group in the molecule and not having an epoxy group, Can improve the compatibility. Moreover, since the photocurable resin composition contains the compound B having moderate hydrophilicity, even if the photocurable resin composition contains the compound A1 that is more hydrophobic than the compound A2, the display element of the photocurable resin composition, in particular, Elution to the liquid crystal can be suppressed. The content mass ratio between the compound A2 and the compound A1 can be, for example, A2 / A1 = 1 / 0.4 to 1 / 0.6.

  The content of the compound A2 having a (meth) acryloyl group and an epoxy group in the molecule is not particularly limited, but may be, for example, 30% by mass or more with respect to the curable compound A.

  The weight average molecular weight of the curable compound A is preferably about 310 to 1,000. The weight average molecular weight of the curable compound A can be measured in terms of polystyrene by, for example, gel permeation chromatography (GPC).

  The content of the curable compound A is preferably 40 to 80% by mass and more preferably 50 to 75% by mass with respect to the photocurable resin composition.

1-2. Compound B
Compound B contained in the photocurable resin composition of the present invention has an anthraquinone skeleton or thioxanthone skeleton and an NHCO group in the molecule.

  The anthraquinone skeleton or thioxanthone skeleton contained in Compound B can absorb and excite light in the visible light region, and can cause a hydrogen abstraction reaction from the curable compound A. Since the NHCO group contained in Compound B exhibits moderate hydrophilicity, the elution of Compound B into the liquid crystal material can be preferably suppressed. Therefore, the compound B can preferably function as a photopolymerization initiator for a photocurable resin composition used as a display element sealant, particularly a liquid crystal sealant.

  The number of anthraquinone skeletons or thioxanthone skeletons per molecule is 1 or 2 or more. Even if the content of Compound B is small, the number of anthraquinone skeletons or thioxanthone skeletons per molecule is preferably 2 or more from the viewpoint of obtaining sufficient curability for light in the visible light region.

  The number of NHCO groups per molecule is 1 or 2 or more. From the viewpoint of highly suppressing the elution of Compound B into the liquid crystal material, the number of NHCO groups per molecule is preferably 2 or more, and more preferably 3 or more. Compound B preferably has a burette skeleton (—NHCO (N—) CONH—) or an allophanate skeleton (—NHCO (N—) COO—) from the viewpoint of easily increasing the number of NHCO groups per molecule. .

  Compound B may further have an ethylenically unsaturated double bond in the molecule. When compound B further has an ethylenically unsaturated double bond in the molecule, for example, compound B and curable compound A undergo a polymerization reaction during curing, and elution of compound B into the liquid crystal material is further suppressed. Cheap.

  Compound B is obtained by reacting “anthraquinone compound b1 having a hydroxy group in the molecule or thioxanthone compound b2 having a hydroxy group in the molecule” with “compound b3 having an isocyanate group in the molecule”.

“Anthraquinone compound b1 having a hydroxy group in the molecule” is represented by the following formula (1). The “thioxanthone compound b2 having a hydroxy group in the molecule” is represented by the following formula (2).

L _{1 in the} formulas (1) and (2) each independently represents a single bond or a divalent organic group. The divalent organic group includes an alkylene group having 1 to 10 carbon atoms (for example, a methylene group and an ethylene group), an alkyleneoxy group having 1 to 10 carbon atoms (for example, a methyleneoxy group and an ethyleneoxy group), 10 alkylenethio groups (for example, methylenethio group (—S—CH ₂ —), ethylenethio group (—S—CH ₂ CH ₂ —), etc.), C 6-10 arylene groups (for example, phenylene group), C 6 -10 aryleneoxy group (for example, phenyleneoxy group) or C6-C10 arylenethio group (for example, phenylenethio group). Among them, when a thioether group (-S-) is bonded to an anthraquinone skeleton or a thioxanthone skeleton, it is easy to absorb light on the long wavelength side, so that an alkylenethio group having 1 to 10 carbon atoms or 6 to 10 carbon atoms is used. An arylenethio group is preferred.

M in the formulas (1) and (2) is an integer of 1 or more, preferably 1. -(L ₁ -OH) may be bonded to any one of the 1st to 8th carbon atoms of the anthraquinone skeleton or thioxanthone skeleton, but is preferably bonded to the 2nd or 7th carbon atom. .

The compound represented by the formula (1) is preferably represented by the following formula (1 ′); the compound represented by the formula (2) is preferably represented by the following formula (2 ′).

-L ₁ -OH in the formulas (1 ′) and (2 ′) may be bonded to any one of the 1st to 8th carbon atoms of the anthraquinone skeleton or thioxanthone skeleton, but the 2nd or 7th carbon. It is preferably bonded to an atom.

  The “compound b3 having an isocyanate group in the molecule” is a compound having one or more isocyanate groups in the molecule. A compound having two or more isocyanate groups in the molecule is preferable in that the NHCO group equivalent of the obtained compound B can be easily adjusted to a certain value or less. The number of isocyanate groups per molecule is not particularly limited, but is preferably 2 to 4 and more preferably 2 to 3 from the viewpoint that the NHCO group equivalent of Compound B can be easily kept below a certain level.

The compound having two or more isocyanate groups in the molecule preferably has an NHCO group in the molecule, and a burette skeleton (—NHCO (N—) CONH—), an allophanate skeleton (—NHCO (N—) COO—) Alternatively, it preferably has a urethane skeleton, and more preferably has a burette skeleton or an allophanate skeleton. That is, a compound having two or more isocyanate groups in the molecule can be represented by, for example, the following formula (3a) or (3b).

（式（γ）のＲ_３は、後述するポリオールに由来する飽和脂肪族炭化水素基又は芳香族炭化水素基を示し、ｎは１以上の整数である）R _{1 in} formula (3a) and R _{2 in} formula (3b) are each a linear, branched or cyclic saturated aliphatic hydrocarbon group or aromatic hydrocarbon group which may have an NHCO group. . The number of NHCO groups contained in R ₁ and R ₂ is 0 or 1 or more, and preferably 2 or more. R ₁ and R ₂ preferably include a structure represented by the following formula (α), (β) or (γ); and may have a structure represented by the following formula (α) or formula (β). More preferred.

(R _{3 in the} formula (γ) represents a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group derived from a polyol described later, and n is an integer of 1 or more)

  The compound having two or more isocyanate groups in the molecule is, for example, a burette body or allophanate body obtained from diisocyanate, or a urethane prepolymer obtained by reacting polyisocyanate and polyol, and having an isocyanate group at the molecular end. It is possible.

  Examples of diisocyanates used as raw materials for burettes or allophanates include aliphatic diisocyanates having 1 to 10 carbon atoms such as tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate; cyclohexylene diisocyanate, hydrogenated C6-C15 alicyclic diisocyanate such as xylylene diisocyanate and isophorone diisocyanate; and C6-C15 such as tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate Aromatic diisocyanates are included.

  The polyisocyanate used as the raw material of the urethane prepolymer is a polyfunctional aliphatic, alicyclic or aromatic isocyanate, and examples thereof include the above-described diisocyanates. Examples of the polyol used as a raw material for the urethane prepolymer include aliphatic polyols such as ethylene glycol, 1,3-propanediol, polyethylene glycol, dipropylene glycol, and pentaerythritol; 1,4-cyclohexanedimethanol, 1,4- Examples include alicyclic polyols such as cyclohexanediol, hydrogenated bisphenol A, and hydrogenated bisphenol F; aromatic polyols such as phenol A and bisphenol F, and the like.

Compound B is preferably obtained by reacting “compound represented by formula (1 ′) or formula (2 ′)” with “compound having two or more isocyanate groups in the molecule”; 1 ′) or a compound represented by formula (2 ′) ”and“ a compound represented by formula (3a) or (3b) (preferably R ₁ or R ₂ has an NHCO group) ” It is more preferable to be obtained.

The following reaction scheme shows an example in which compound B is obtained by reacting a compound represented by formula (1 ′) with a compound represented by formula (3b).

  In addition to the reaction of “compound represented by formula (1 ′) or formula (2 ′)” and “compound having two or more isocyanate groups in the molecule”, “hydroxy group-containing compound b4” is further added. You may make it react.

  “Hydroxy group-containing compound b4” is a compound having a hydroxy group in the molecule. The hydroxy group of the compound having a hydroxy group in the molecule can react with the isocyanate group of the “compound having two or more isocyanate groups in the molecule” to further form —O—CONH—. Examples of the compound having a hydroxy group in the molecule include monoalcohols having 1 to 20 carbon atoms such as methanol, ethanol, propanol, butanol, pentanol, hexanol, and 1-octadecanol.

  The compound having a hydroxy group in the molecule may further have an ethylenically unsaturated double bond. Thereby, an ethylenically unsaturated double bond can be introduced into the compound B. Examples of the hydroxy group-containing compound having an ethylenically unsaturated double bond in the molecule include (meth) acrylate substituted with a hydroxy group such as 4-hydroxybutyl acrylate.

Especially, it is preferable that the compound B is represented by following formula (4) or (5).

_{L 1} of formula (4) and (5) are the same meaning as _{L 1} in formula (1) and (2).

  X in the formulas (4) and (5) represents an organic group derived from a compound having at least p isocyanate groups in the molecule. The group derived from a compound having at least p isocyanate groups in the molecule is preferably a group derived from a compound having two or more isocyanate groups in the molecule, and is represented by the formula (3a). More preferably, it is a divalent group derived from the compound represented by formula (3b) or a trivalent group derived from the compound represented by formula (3b).

  P of Formula (4) and (5) represents the integer of 1-5, Preferably it is 2 or 3.

The group represented by —L ₁ —O—X may be bonded to any one of the 1st to 8th carbon atoms of the anthraquinone skeleton or thioxanthone skeleton, but is bonded to the 2nd or 7th carbon atom. It is preferable.

  Specific examples of compound B include a compound obtained by reacting 2- (2-hydroxyethylthio) -9,10-anthraquinone with a modified product of hexamethylene diisocyanate biuret, 2-hydroxymethylanthraquinone and modified with hexamethylene diisocyanate biuret. A compound obtained by reacting with a compound, a compound obtained by reacting 2- (2-hydroxyethylthio) -9,10-anthraquinone with a modified product of hexamethylene diisocyanate allophanate, 2-hydroxythioxanthone and hexamethylene diisocyanate biuret A compound obtained by reacting a modified product, a compound obtained by reacting 2-hydroxythioxanthone and a hexamethylene diisocyanate allophanate modified product, 2- (2-hydroxyethylthio) -thioxanthen-9-one and Compounds obtained by reacting xamethylene diisocyanate biuret modified products, compounds obtained by reacting 2- (2-hydroxyethylthio) -thioxanthen-9-one with hexamethylene diisocyanate allophanate modified products, and these A compound obtained by further reacting a compound with octadecanol or 4-hydroxybutyl acrylate is included.

  In order to suppress the contamination of the liquid crystal material by the compound B, it is conceivable to increase the molecular weight of the compound B. However, merely increasing the molecular weight of Compound B may relatively reduce the content ratio per molecule of anthraquinone skeleton or thioxanthone skeleton that contributes to light absorption. As a result, it is necessary to increase the content of compound B in order to obtain a certain level of light absorptivity, which may cause contamination of the liquid crystal material. Therefore, in the present invention, it is preferable to set the ratio of NHCO groups contained in one molecule to a certain value or more (make the NHCO group equivalent to a certain value or less).

That is, the NHCO group equivalent of Compound B is preferably 350 g / eq or less. If the NHCO group equivalent of Compound B is 350 g / eq or less, the number of NHCO groups contained in Compound B is relatively large, so that the hydrophilicity is moderately increased and the photocurable resin composition is used as a liquid crystal sealant. Elution of the compound B into the liquid crystal material can be suppressed. The NHCO group equivalent of Compound B is more preferably 200 to 350 g / eq, and further preferably 230 to 330 g / eq. When the NHCO group equivalent of Compound B is 200 g / eq or more, the moisture resistance of the cured product of the photocurable resin composition is hardly impaired. The NHCO group equivalent of compound B is defined by the following formula (I).
NHCO group equivalent (g / eq) = molecular weight / number of NHCO groups contained in one molecule: Formula (I)

In order to make the NHCO group equivalent of the compound B within the above range, as described above, “the compound represented by the formula (1 ′) or the formula (2 ′)” and “the compound having two or more isocyanate groups in the molecule” It is preferable to react; “compound represented by Formula (1 ′) or Formula (2 ′)” and “compound represented by Formula (3a) or (3b) (preferably R ₁ or R ₂ It is preferable to react with those having an NHCO group.

  The molecular weight of Compound B is preferably 500 or more and 5000 or less, for example. The “molecular weight” of compound B is the “relative molecular mass” of the molecular structure of the main peak when a main peak is detected when high performance liquid chromatography (HPLC) is performed under the following conditions. When the main peak is not detected, the weight average molecular weight is assumed.

Specifically, Compound B is dissolved in THF (tetrahydrofuran) to prepare a sample solution, and high performance liquid chromatography (HPLC) measurement is performed under the following measurement conditions. And the presence or absence of the main peak (main detection peak) is confirmed in the peak detected with the detection wavelength of 400 nm. “Main peak (main detection peak)” refers to a peak having the highest intensity (peak having the highest peak height) among all peaks detected at a detection wavelength of 400 nm.
(HPLC measurement conditions)
Equipment: Acquity TM UPLC H-Class system made by waters
Column: Acquity UPLC BEH C18, 2.1 mm ID × 100 mm Particle size: 1.7 μm
Mobile phase: A: Acetonitrile
B: 5 mM ammonium acetate aqueous solution
A / B = 60/40 (0-4 minutes)
95/5 (4-9 minutes)
95/5 (9-10 minutes)
Flow rate: 0.4mL / min
PDA detector: Measurement wavelength: 190-500nm, Extraction wavelength: 400nm

Next, the relative molecular mass corresponding to the peak apex of the detected main peak is measured by liquid chromatography mass spectrometry (LC / MS).
(LC / MS measurement conditions)
Equipment: Acquity TM H-Class system / SQ Detector made by waters
Column: Acquity UPLC BEH C18, 2.1mmID × 100mm Particle size: 1.7μm
Mobile phase: A: Acetonitrile
B: 5 mM ammonium acetate aqueous solution
A / B = 60/40 (0-4 minutes)
95/5 (4-9 minutes)
95/5 (9-10 minutes)
Flow rate: 0.4 mL / min Ionization: ESI (electrospray ionization), positive / negative ion measurement
PDA detector: Measurement wavelength: 190-500nm, Extraction wavelength: 400nm

  The weight average molecular weight of compound B can be measured in terms of standard polystyrene by a gel permeation chromatography (GPC) method.

  If the molecular weight of compound B is 500 or more, it is difficult to dissolve in liquid crystal, and thus liquid crystal contamination can be easily reduced. When the molecular weight of the compound B is 5000 or less, the compatibility with the curable compound A is hardly impaired. The molecular weight of Compound B is more preferably 500 or more and 3000 or less, and further preferably 700 or more and 1500 or less.

The NHCO group equivalent of compound B can be confirmed by combining high performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC / MS) with NMR measurement or IR measurement. Specifically, the following procedure can be used.
1) A solution in which a photocurable resin composition is dissolved in tetrahydrofuran (THF) is centrifuged by a centrifugal separator to precipitate particle components such as silica particles and thermoplastic resin particles. The obtained solution is filtered through a filter to remove the particle component, thereby obtaining a sample solution.
2) The sample solution obtained in 1) is subjected to high performance liquid chromatography (HPLC) measurement. The HPLC measurement methods and conditions are the same as the HPLC measurement methods and conditions in the measurement of the molecular weight of Compound B.
Next, in HPLC measurement, the relative molecular mass and the composition formula of the main peak detected by a detector having a wavelength of 400 nm characteristic of the anthraquinone skeleton or thioxanthone skeleton are analyzed by liquid chromatography mass spectrometry (LC / MS ) To measure. The LC / MS measurement method and conditions are the same as the LC / MS measurement method and conditions in the measurement of the molecular weight of Compound B.
3) On the other hand, NMR measurement or IR measurement is performed on the sample solution obtained in 1). Thereby, the presence or absence of a spectrum characteristic of the anthraquinone skeleton or thioxanthone skeleton or NHCO group is confirmed, and the chemical structure is specified.
4) The molecular weight obtained in 2) above and the number of NHCO groups obtained in 3) above are applied to the above formula (I) to obtain the NHCO group equivalent (g / eq).

  Compound B may be one type or a combination of two or more types. For example, a compound having an anthraquinone skeleton in the molecule and a compound having a thioxanthone skeleton in the molecule may be combined.

  The content of compound B is preferably 0.01 to 10% by mass with respect to curable compound A. If the content of Compound B is 0.01% by mass or more, sufficient photocurability is easily obtained. When the content of Compound B is 10% by mass or less, elution into the liquid crystal material is unlikely to occur, and sufficient photocurability is easily obtained.

In particular, when the compound B is a compound having an anthraquinone skeleton in the molecule, the content of the compound B is more preferably 0.1 to 5% by mass with respect to the curable compound A. It is more preferable that it is 3 mass%, and it is especially preferable that it is 0.1 to 2 mass%.
Moreover, when the compound B is a compound having a thioxanthone skeleton in the molecule, the content of the compound B is more preferably 0.1 to 6% by mass with respect to the curable compound A, and 0.1% by mass. % Or more and less than 4% by mass.

1-3. Thermosetting compound C
The thermosetting compound C is preferably an epoxy compound having an epoxy group in the molecule. However, the thermosetting compound C is different from the curable compound A. The thermosetting compound C is more preferably an epoxy compound having no (meth) acryloyl group in the molecule. The epoxy compound may be any of a monomer, an oligomer or a polymer. Epoxy compounds, for example, have low solubility and diffusibility in liquid crystal when using a photocurable resin composition as a liquid crystal sealant, and not only improve the display characteristics of the resulting liquid crystal panel, but also the moisture resistance of the cured product. Can improve sex.

  The epoxy compound may be an aromatic epoxy compound having a weight average molecular weight of 500 to 10000, preferably 1000 to 5000. The weight average molecular weight of the epoxy compound can be measured in terms of polystyrene by gel permeation chromatography (GPC).

  Examples of aromatic epoxy compounds include the reaction of aromatic diols typified by bisphenol A, bisphenol S, bisphenol F, bisphenol AD, etc., and diols modified with ethylene glycol, propylene glycol, alkylene glycol, and epichlorohydrin. Aromatic polyvalent glycidyl ether compound obtained by the above; novolak type obtained by reaction of novolak resin derived from phenol or cresol and formaldehyde, polyphenols typified by polyalkenylphenol and copolymers thereof, and epichlorohydrin Polyvalent glycidyl ether compounds; xylylene phenol resin glycidyl ether compounds and the like are included. Among them, cresol novolac type epoxy compound, phenol novolac type epoxy compound, bisphenol A type epoxy compound, bisphenol F type epoxy compound, triphenolmethane type epoxy compound, triphenolethane type epoxy compound, trisphenol type epoxy compound, dicyclopentadiene type Epoxy compounds, diphenyl ether type epoxy compounds and biphenyl type epoxy compounds are preferred. The epoxy compound may be one type or a combination of two or more types.

  The epoxy compound may be liquid or solid. A solid epoxy compound is preferable from the viewpoint of easily improving the moisture resistance of the cured product. The softening point of the solid epoxy compound is preferably 40 ° C. or higher and 150 ° C. or lower. The softening point can be measured by the ring and ball method defined in JIS K7234.

  It is preferable that content of the thermosetting compound C is 3-20 mass% with respect to a photocurable resin composition. When the content of the thermosetting compound C with respect to the photocurable resin composition is 3% by mass or more, the moisture resistance of the cured product of the photocurable resin composition can be easily improved. When the content of the thermosetting compound C with respect to the photocurable resin composition is 20% by mass or less, an excessive increase in the viscosity of the photocurable resin composition can be suppressed. As for content of the thermosetting compound C, it is more preferable that it is 3-15 mass% with respect to a photocurable resin composition, and it is further more preferable that it is 4-15 mass%.

  It is preferable that content of the thermosetting compound C is 3.8-50 mass% with respect to the curable compound A, and it is more preferable that it is 5-30 mass%. When the content of the thermosetting compound C with respect to the curable compound A is 5% by mass or more, the moisture resistance of the cured product and the adhesive strength to the glass substrate can be further enhanced. The compatibility with the conductive compound A tends to be further improved.

1-4. Thermosetting agent D
The thermosetting agent D is a compound that does not cure the thermosetting compound C under normal storage conditions (room temperature, under visible light, etc.), but cures the compound when given heat. The photocurable resin composition containing the thermosetting agent D is excellent in storage stability and excellent in thermosetting. The thermosetting agent D is preferably an epoxy curing agent.

  Epoxy curing agent is an epoxy curing agent having a melting point of 50 ° C. or more and 250 ° C. or less, although it depends on the heat curing temperature from the viewpoint of enhancing the viscosity stability of the photo-curable resin composition and not impairing the moisture resistance of the cured product. An epoxy curing agent having a melting point of 100 ° C. or higher and 200 ° C. or lower is more preferable, and an epoxy curing agent having a melting point of 150 ° C. or higher and 200 ° C. or lower is further preferable.

  Examples of epoxy curing agents include organic acid dihydrazide thermal latent curing agents, imidazole thermal latent curing agents, dicyandiamide thermal latent curing agents, amine adduct thermal latent curing agents, and polyamine thermal latent curing. Agent is included.

  Examples of organic acid dihydrazide thermal latent curing agents include adipic acid dihydrazide (melting point 181 ° C.), 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (melting point 120 ° C.), 7,11-octa Decadiene-1,18-dicarbohydrazide (melting point 160 ° C.), dodecanedioic acid dihydrazide (melting point 190 ° C.), sebacic acid dihydrazide (melting point 189 ° C.) and the like. Examples of imidazole-based thermal latent curing agents include 2,4-diamino-6- [2′-ethylimidazolyl- (1 ′)]-ethyltriazine (melting point: 215 to 225 ° C.) and 2-phenylimidazole (melting point) 137-147 ° C.) and the like. Examples of the dicyandiamide-based heat latent curing agent include dicyandiamide (melting point: 209 ° C.). The amine adduct thermal latent curing agent is a thermal latent curing agent comprising an addition compound obtained by reacting an amine compound having catalytic activity with an arbitrary compound, and examples thereof include Ajinomoto Fine Techno Co., Ltd. ) Amicure PN-40 (melting point 110 ° C.), Ajinomoto Fine Techno Co., Ltd. Amicure PN-23 (melting point 100 ° C.), Ajinomoto Fine Techno Co., Ltd. Amicure PN-31 (melting point 115 ° C.), Ajinomoto Fine Techno ( Amicure PN-H (melting point: 115 ° C.) manufactured by Ajinomoto Fine Techno Co., Ltd. Amycure MY-24 (melting point: 120 ° C.), Amicure MY-H (melting point: 131 ° C.) manufactured by Ajinomoto Fine Techno Co., etc. It is. The polyamine thermal latent curing agent is a thermal latent curing agent having a polymer structure obtained by reacting an amine and an epoxy. Examples thereof include Adeka Hardener EH4339S (softening point 120 to 130, manufactured by ADEKA Corporation). ° C), and ADEKA Corporation ADEKA HARDNER EH4357S (softening point 73-83 ° C). Of these, dihydrazide thermal latent curing agents, imidazole thermal latent curing agents, amine adduct thermal latent curing agents, and polyamine thermal latent curing agents are preferred. The epoxy curing agent may be only one type or a combination of two or more types.

  The content of the thermosetting agent D is preferably 3 to 30% by mass, more preferably 3 to 20% by mass, and 5 to 20% by mass with respect to the photocurable resin composition. Further preferred. The photocurable resin composition containing the thermosetting agent D can be a one-component curable resin composition. The one-component curable resin composition is excellent in workability because it is not necessary to mix the main agent and the curing agent in use.

  The content of the thermosetting agent D is preferably 3.8 to 75% by mass with respect to the curable compound A, more preferably 3.8 to 50% by mass, and 10 to 40% by mass. More preferably. When the content of the thermosetting agent D with respect to the curable compound A is 10% by mass or more, the curability of the curable compound A at the time of heating is further enhanced, and when it is 40% by mass or less, liquid crystal contamination is further suppressed. It's easy to do.

  The total content of the thermosetting compound C and the thermosetting agent D is preferably 6 to 50% by mass, more preferably 6 to 35% by mass, and more preferably 6 to 35% by mass with respect to the photocurable resin composition. More preferably, it is 30 mass%.

1-5. Other ingredients E
1-5-1. Thermoplastic polymer fine particles
The photocurable resin composition of the present invention may further contain thermoplastic polymer fine particles as necessary. The thermoplastic polymer fine particles contain a thermoplastic polymer having a softening point temperature of 50 to 120 ° C., preferably 70 to 100 ° C. as measured by a ring and ball method, and a number average particle size of 0.05 to 5 μm, preferably 0.8. It may be 1 to 3 μm. The photocurable resin composition containing such thermoplastic polymer fine particles can relieve the shrinkage stress generated in the cured product. Moreover, when the number average particle diameter is set to the upper limit value or less, it is possible to prevent the coating stability from being lowered by the thermoplastic polymer fine particles when forming a seal member having a narrow line width. The number average particle diameter can be measured with a dry particle size distribution meter.

  Examples of the thermoplastic polymer fine particles include fine particles obtained by suspension polymerization of a resin containing an epoxy group and a double bond group with a monomer capable of radical polymerization. Examples of the resin containing an epoxy group and a double bond group include a resin obtained by reacting a bisphenol F type epoxy resin and methacrylic acid in the presence of a tertiary amine. Examples of radically polymerizable monomers include butyl acrylate, glycidyl methacrylate, and divinylbenzene.

  The content of the thermoplastic polymer fine particles is preferably 5 to 40% by mass and more preferably 7 to 30% by mass with respect to the photocurable resin composition. When the content of the thermoplastic polymer fine particle is within the above range, the thermoplastic polymer fine particle can preferably relieve the shrinkage stress during the heat curing of the photocurable resin composition, and can easily form a seal member with a desired line width. .

1-5-2. Filler The photocurable resin composition of the present invention may further contain a filler as necessary. A photocurable resin composition containing a filler may have good viscosity, strength of a cured product, linear expansion, and the like.

Examples of fillers include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, titanium nitride, aluminum oxide (alumina), zinc oxide, silicon dioxide, potassium titanate, Inorganic fillers such as kaolin, talc, glass beads, sericite , activated clay, bentonite, aluminum nitride, silicon nitride are included. Of these, silicon dioxide and talc are preferable.

The shape of the filler may be a regular shape such as a spherical shape, a plate shape, or a needle shape, or may be an irregular shape. When the filler is spherical, the average primary particle diameter of the filler is preferably 1.5 μm or less, and the specific surface area is preferably 0.5 to ²⁰ m ² / g. The average primary particle diameter of the filler can be measured by a laser diffraction method described in JIS Z8825-1. The specific surface area of the filler can be measured by the BET method described in JIS Z8830.

  It is preferable that content of a filler is 1-45 mass% with respect to a photocurable resin composition. When the content of the filler is 1% by mass or more, it is easy to improve the moisture resistance of the cured product of the photocurable resin composition, and when it is 45% by mass or less, the coating stability of the photocurable resin composition is improved. Hard to be damaged. As for content of a filler, it is more preferable that it is 10-30 mass% with respect to a photocurable resin composition.

  The photocurable resin composition of the present invention includes a thermal radical polymerization initiator, a coupling agent such as a silane coupling agent, an ion trapping agent, an ion exchange agent, a leveling agent, a pigment, a dye, a sensitizer, as necessary. Additives such as plasticizers and antifoaming agents may further be included.

  Examples of the silane coupling agent include vinyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and the like. The content of the silane coupling agent may be 0.01 to 5% by mass with respect to the curable compound A. When the content of the silane coupling agent is 0.01% by mass or more, the cured product of the photocurable resin composition tends to have sufficient adhesiveness.

  The photocurable resin composition of the present invention may further include a spacer for adjusting the gap of the liquid crystal display panel.

  The total content of other components E is preferably 1 to 50% by mass with respect to the photocurable resin composition. When the total content of other components E is 50% by mass or less, the viscosity of the photocurable resin composition is hardly excessively increased, and the coating stability is not easily impaired.

1-6. Physical Properties of Photocurable Resin Composition The viscosity of the photocurable resin composition of the present invention at 25 ° C. and 2.5 rpm of the E-type viscometer is preferably 200 to 450 Pa · s, and preferably 300 to 400 Pa · s. It is more preferable that When the viscosity is in the above range, the applicability of the photocurable resin composition by the dispenser is good.

  The photocurable resin composition of the present invention can be used as, for example, a sealing agent. The sealing agent is preferably a display element sealing agent used for sealing display elements such as liquid crystal display elements, organic EL elements, and LED elements. The display element sealant is particularly preferably a liquid crystal sealant and more preferably a liquid crystal sealant for a liquid crystal dropping method because the photocurable resin composition of the present invention can satisfactorily suppress liquid crystal contamination. preferable.

  Compound B contained in the photocurable resin composition of the present invention exhibits good light absorption even for light having a long wavelength, so that curing in a short time while reducing damage to the liquid crystal layer due to light. Is possible. In addition, since compound B contains a relatively large number of NHCO groups per molecule, it has moderate hydrophilicity and can highly suppress elution into the liquid crystal material.

2. Liquid crystal display panel and manufacturing method thereof The display element panel of the present invention includes a pair of substrates, a display element disposed between the pair of substrates, and a seal member for sealing the display element. The seal member can be a cured product of the display element sealant of the present invention. The display element sealing agent of the present invention is composed of the photocurable resin composition of the present invention.

  Examples of display elements include liquid crystal display elements, organic EL elements, LED elements, and the like. Among these, a liquid crystal display element is preferable because the photocurable resin composition of the present invention can satisfactorily suppress liquid crystal contamination.

  That is, the liquid crystal display panel of the present invention includes a display substrate, a counter substrate that is paired with the display substrate, a frame-shaped sealing member disposed between the display substrate and the counter substrate, and a space between the display substrate and the counter substrate. And a liquid crystal layer filled in a space surrounded by the seal member. The seal member can be a cured product of the liquid crystal sealant of the present invention. The liquid crystal sealing agent of the present invention comprises the photocurable resin composition of the present invention.

  Both the display substrate and the counter substrate are transparent substrates. The material of the transparent substrate can be glass or plastic such as polycarbonate, polyethylene terephthalate, polyethersulfone and PMMA.

  Matrix TFTs, color filters, black matrices, and the like can be disposed on the surface of the display substrate or the counter substrate. An alignment film may be further disposed on the surface of the display substrate or the counter substrate. The alignment film contains a known organic alignment agent or inorganic alignment agent.

  The liquid crystal display panel is manufactured using the liquid crystal sealant of the present invention. Generally, there are a liquid crystal dropping method and a liquid crystal injecting method as a method for manufacturing a liquid crystal display panel, but the liquid crystal display panel of the present invention is preferably manufactured by a liquid crystal dropping method.

The manufacturing method of the liquid crystal display panel by the liquid crystal dropping method is
1) forming a seal pattern of the liquid crystal sealant of the present invention on one substrate;
2) a step of dropping liquid crystal in a region surrounded by the seal pattern of the substrate or a region of the other substrate facing the region surrounded by the seal pattern when the seal pattern is in an uncured state;
3) a step of superimposing one substrate and the other substrate through a seal pattern;
4) curing the seal pattern.

  In the step 2), the uncured state of the seal pattern means a state in which the curing reaction of the liquid crystal sealant has not progressed to the gel point. For this reason, in the step 2), in order to suppress dissolution of the liquid crystal sealant in the liquid crystal, the seal pattern may be semi-cured by light irradiation or heating. One substrate and the other substrate are a display substrate and a counter substrate, respectively.

  In the step 4), only curing by light irradiation may be performed, but after curing by light irradiation, curing by heating may be performed. Since the liquid crystal sealant can be cured in a short time by curing by light irradiation, dissolution in the liquid crystal can be suppressed. By combining curing by light irradiation and curing by heating, damage to the liquid crystal layer due to light can be reduced compared to the case of only curing by light irradiation.

  The light to be irradiated is preferably light having a wavelength of 370 to 450 nm. This is because the light having the above wavelength causes relatively little damage to the liquid crystal material and the drive electrode. For light irradiation, a known light source that emits ultraviolet light or visible light can be used. For irradiation with visible light, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, or the like can be used.

  The light irradiation energy may be energy that can cure the curable compound A. The photocuring time is, for example, about 10 minutes although it depends on the composition of the liquid crystal sealant.

  The thermosetting temperature is 120 ° C., for example, although it depends on the composition of the liquid crystal sealant, and the thermosetting time is about 2 hours.

  The liquid crystal sealant of the present invention has reduced dissolution in liquid crystals. Therefore, a liquid crystal display panel having a cured product of the liquid crystal sealant of the present invention is less contaminated with liquid crystals and can have high quality display performance.

  In the following, the invention will be described in more detail with reference to examples. These examples do not limit the scope of the present invention.

1. Synthesis and Evaluation of Compound B and Comparative Compound (1) Synthesis (Synthesis Example 1)
2. Hexamethylene diisocyanate biuret modified (manufactured by Mitsui Chemicals, Takenate D-165N, isocyanate equivalent 179.5 g / eq) into a four-necked flask equipped with a stirrer, nitrogen gas inlet tube, reflux condenser, and thermometer. 16 g and 40 g of toluene were added and stirred at 80 ° C. Next, a solution in which 2.50 g (8.80 × 10 ⁻³ mol) of 2- (2-hydroxyethylthio) -9,10-anthraquinone was dissolved in 100 g of toluene was added, and one drop was added using dibutyltin as a catalyst. Thereafter, the mixture was stirred as it was at 80 ° C. for 1 hour in a nitrogen atmosphere.
After confirming disappearance of 2- (2-hydroxyethylthio) -9,10-anthraquinone by thin layer chromatography (TLC), 1.27 g of 4-hydroxybutyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 5 g of toluene. The solution dissolved in was further added dropwise and stirred at 80 ° C. for 1 hour in the atmosphere. After completion of the reaction, the four-necked flask was allowed to cool at room temperature, and the precipitated crystal component was separated. The obtained crystal component was again mixed with toluene, stirred at 100 ° C. for 1 hour, and then ice-cooled again to remove impure components. The recovered crystal component was sufficiently dried in an oven to obtain Compound B-1.

(Synthesis Example 2)
Into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer, 0.5 g (2.1 × 10 ⁻³ mol) of 2-hydroxymethylanthraquinone (manufactured by Junsei Kagaku) and 20 g of toluene After stirring at 90 ° C., 1 drop of dibutyltin was added as a catalyst. Next, a hexamethylene diisocyanate biuret modified product (manufactured by Mitsui Chemicals, Takenate D-165N, isocyanate equivalent 179.5 g / eq) 0.45 g dissolved in toluene 10 g was added dropwise over 20 minutes, and then a nitrogen atmosphere as it was The mixture was stirred at 80 ° C. for 2 hours. After completion of the reaction, the four-necked flask was cooled in an ice bath, and the precipitated crystal components were separated. The obtained crystal component was again mixed with toluene, stirred at 90 ° C. for 1 hour, and then ice-cooled again to remove impure components. The recovered crystal component was sufficiently dried in an oven to obtain Compound B-2.

(Synthesis Example 3)
5.00 g ( 1.76 × 10 ⁻² mol) of 2- (2-hydroxyethylthio) -9,10-anthraquinone into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer ) And 150 g of toluene were added and stirred at 80 ° C., and 1 drop of dibutyltin was added as a catalyst. Subsequently, a solution prepared by dissolving 3.79 g of a hexamethylene diisocyanate biuret modified product (manufactured by Mitsui Chemicals, Takenate D-165N, isocyanate equivalent 179.5 g / eq) in 10 g of toluene was dropped over 30 minutes. After completion of the dropwise addition, the mixture was stirred at 80 ° C. for 3 hours under a nitrogen atmosphere, and then 10.6 g of isopropyl alcohol was added and the mixture was stirred as it was for 2 hours. After completion of the reaction, the four-necked flask was cooled in an ice bath to separate the crystal component. The obtained crystal component was again mixed with toluene, stirred at 100 ° C. for 1 hour, and then ice-cooled again to remove impure components. The recovered crystal component was sufficiently dried in an oven to obtain Compound B-3.

(Synthesis Example 4)
Into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer, 3.0 g (1.06 × 10 ⁻² mol) of 2- (2-hydroxyethylthio) -9,10-anthraquinone And 100 g of toluene were added and stirred at 110 ° C., and 1 drop of dibutyltin was added as a catalyst. Subsequently, a solution prepared by dissolving 2.95 g of a hexamethylene diisocyanate biuret modified product (manufactured by Mitsui Chemicals, Takenate D-165N, isocyanate equivalent 179.5 g / eq) in 10 g of toluene was added dropwise over 30 minutes.
After confirming the disappearance of 2- (2-hydroxyethylthio) -9,10-anthraquinone by thin layer chromatography (TLC), 1.43 g of 1-octadecanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 10 g of toluene. The solution dissolved in was further added dropwise and stirred at 110 ° C. for 2 hours under a nitrogen atmosphere. After completion of the reaction, the four-necked flask was cooled in an ice bath, and the precipitated crystal components were separated. The obtained crystal component was again mixed with toluene, stirred at 100 ° C. for 1 hour, and then ice-cooled again to remove impure components. The crystal component recovered by filtration was sufficiently dried in an oven to obtain Compound B-4.

(Synthesis Example 5)
Into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer, 5.0 g (1.76 × 10 ⁻² mol) of 2- (2-hydroxyethylthio) -9,10-anthraquinone ) And 150 g of toluene were added and stirred at 80 ° C., and 1 drop of dibutyltin was added as a catalyst. Next, a hexamethylene diisocyanate allophanate modified product (manufactured by Mitsui Chemicals, Takenate D-178NL, isocyanate equivalent 216.1 g / eq) of 3.98 g dissolved in 10 g of toluene was added dropwise over 30 minutes, and then a nitrogen atmosphere as it was The mixture was stirred at 80 ° C. for 2 hours. After completion of the reaction, the four-necked flask was cooled in an ice bath, and the precipitated crystal components were separated. The obtained crystal component was again mixed with toluene, stirred at 100 ° C. for 1 hour, and then ice-cooled again to remove impure components. The recovered crystal component was sufficiently dried in an oven to obtain Compound B-5.

(Synthesis Example 6)
2- (2-hydroxyethylthio) -9,10-anthraquinone 1.0 g (3.52 × 10 ⁻³ mol) into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer And 70 g of ethyl acetate were added and stirred at 70 ° C., and 1 drop of dibutyltin was added as a catalyst. Next, a solution prepared by dissolving 0.28 g of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 10 g of ethyl acetate was added dropwise over 10 minutes, and then stirred at 70 ° C. for 1 hour in a nitrogen atmosphere. After completion of the reaction, the four-necked flask was allowed to cool at room temperature, and the precipitated crystal component was separated. The obtained crystal component was again mixed with ethyl acetate, stirred at 80 ° C. for 1 hour, and then cooled with ice to remove impure components. The recovered crystal component was sufficiently dried in an oven to obtain Compound R-1.

(Synthesis Example 7)
In a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer, 10.0 g (3.52 × 10 ⁻² mol) of 2- (2-hydroxyethylthio) -9,10-anthraquinone And 150 g of methyl isobutyl ketone were added and stirred at 80 ° C., and 1 drop of dibutyltin was added as a catalyst. Next, a solution prepared by dissolving 5.53 g of dicyclohexylmethane 4,4′-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 25 g of methyl isobutyl ketone was added dropwise over 30 minutes, and then, as it was at 80 ° C. for 3 hours in a nitrogen atmosphere. Stir. After completion of the reaction, the four-necked flask was cooled in an ice bath, and the precipitated crystal components were separated. The obtained crystal component was again mixed with toluene, stirred at 100 ° C. for 1 hour, and then ice-cooled again to remove impure components. The recovered crystal component was sufficiently dried in an oven to obtain Compound R-2.

(Synthesis Example 8)
Into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer, 5.0 g (1.76 × 10 ⁻² mol) of 2- (2-hydroxyethylthio) -9,10-anthraquinone. ) And 150 g of toluene were added and stirred at 80 ° C., and 1 drop of dibutyltin was added as a catalyst. Subsequently, a solution prepared by dissolving 5.25 g (2.20 × 10 ⁻² mol) of 1,1- (bisacryloyloxymethyl) ethyl isocyanate (manufactured by Showa Denko KK, Karenz BEI) in 10 g of toluene was dropped over 30 minutes. Thereafter, the mixture was stirred as it was at 80 ° C. for 2 hours under a nitrogen atmosphere. After completion of the reaction, toluene was distilled off using an evaporator. To the residue, 70 g of toluene and 20 g of ethyl acetate were added and dissolved uniformly, and washed 10 times with 40 g of ultrapure water. After washing with water, the solvent was distilled off again using an evaporator to obtain Compound R-3.

(Synthesis Example 9)
Into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer, 3.43 g (1.21 × 10 ⁻² mol) of 2- (2-hydroxyethylthio) -9,10-anthraquinone ) And 12.15 g of one-component polyurethane resin (Mitsui Chemicals, Takenate M-631N, NCO% = 4.58%, weight average molecular weight 17000, solvent: ethyl acetate / methyl ethyl ketone), and stirred at 80 ° C. Further, 30 g of methyl ethyl ketone was added to obtain a uniform solution. Next, dibutyltin dissolved in toluene was added dropwise as a catalyst, and the mixture was stirred at 80 ° C. for 2 hours in a nitrogen atmosphere. After completion of the reaction, the four-necked flask was cooled in an ice bath, and the precipitated crystal components were separated. The obtained crystal component was again mixed with toluene, stirred at 100 ° C. for 1 hour, and then ice-cooled again to remove impure components. The recovered crystal component was sufficiently dried in an oven to obtain Compound R-4.

(Synthesis Example 10)
5.6 g (0.0225 mol) of 2-chlorothioxanthone and 2.6 g (0.0225 mol) of 2-mercaptoethanol potassium salt in 100 ml of 20 ml of N, N-dimethylacetamide Stir for 18 hours. The resulting reaction mixture was then added to 2N hydrochloric acid and extracted with ethyl acetate. After conventional work-up and chromatographic purification of the extract, 3.5 g of 2- (2-hydroxyethylthio) -thioxanthen-9-one was obtained.

(Synthesis Example 11)
2- (2-hydroxyethylthio) -thioxanthen-9-one synthesized in Synthesis Example 10 into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer (5.00 g (1 .74 × 10 ⁻² mol) and 50 g of toluene were added and stirred at 80 ° C., and then 1 drop of dibutyltin was added as a catalyst. Next, a hexamethylene diisocyanate biuret modified product (Mitsui Chemicals, Takenate D-165N, isocyanate equivalent 179.5 g / eq) 2.08 g dissolved in toluene 10 g was added dropwise over 30 minutes and left under a nitrogen atmosphere. Stir at 80 ° C. for 3 hours.
After confirming the disappearance of 2- (2-hydroxyethylthio) -thioxanthone by thin layer chromatography (TLC), 0.84 g of 4-hydroxybutyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 5 g of toluene. The solution was further added dropwise and stirred at 80 ° C. for 1 hour in the atmosphere. After completion of the reaction, the four-necked flask was allowed to cool at room temperature, and the precipitated solid component was separated. The collected solid component was sufficiently dried in an oven to obtain Compound B-6.

(Synthesis Example 12)
2- (2-hydroxyethylthio) -thioxanthen-9-one synthesized in Synthesis Example 10 into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer (5.00 g (1 .74 × 10 ⁻² mol) and 50 g of toluene were added and stirred at 80 ° C., and then 1 drop of dibutyltin was added as a catalyst. Subsequently, a solution obtained by dissolving 3.74 g of a hexamethylene diisocyanate biuret modified product (manufactured by Mitsui Chemicals, Takenate D-165N, isocyanate equivalent 179.5 g / eq) in 10 g of toluene was dropped over 30 minutes. After completion of the dropwise addition, the mixture was stirred at 80 ° C. for 3 hours in a nitrogen atmosphere, and then 1.04 g of isopropyl alcohol was added and stirred as it was for 2 hours. After completion of the reaction, the four-necked flask was allowed to cool at room temperature to separate the solid components. The collected solid component was sufficiently dried in an oven to obtain Compound B-7.

(Synthesis Example 13)
2- (2-hydroxyethylthio) -thioxanthen-9-one synthesized in Synthesis Example 10 into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer (5.00 g (1 .74 × 10 ⁻² mol) and 50 g of toluene were added and stirred at 80 ° C., and then 1 drop of dibutyltin was added as a catalyst. Next, a hexamethylene diisocyanate biuret modified product (Mitsui Chemicals, Takenate D-165N, isocyanate equivalent 179.5 g / eq) 2.08 g dissolved in toluene 10 g was added dropwise over 30 minutes and left under a nitrogen atmosphere. Stir at 80 ° C. for 3 hours.
After confirming the disappearance of 2- (2-hydroxyethylthio) -thioxanthone by thin layer chromatography (TLC), 1.57 g of 1-octadecanol (Tokyo Chemical Industry Co., Ltd.) was dissolved in 5 g of toluene. The solution was further added dropwise and stirred at 80 ° C. for 1 hour in the atmosphere. After completion of the reaction, the four-necked flask was allowed to cool at room temperature, and the precipitated solid component was separated. The collected solid component was sufficiently dried in an oven to obtain Compound B-8.

(Synthesis Example 14)
2- (2-hydroxyethylthio) -thioxanthen-9-one synthesized in Synthesis Example 10 into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer (5.00 g (1 .74 × 10 ⁻² mol) and 50 g of toluene were added and stirred at 80 ° C., and then 1 drop of dibutyltin was added as a catalyst. Next, a solution in which 4.51 g of hexamethylene diisocyanate allophanate modified product (Mitsui Chemicals, Takenate D-178NL, isocyanate equivalent 216.1 g / eq) was dissolved in 10 g of toluene was dropped over 30 minutes, and the solution was left under a nitrogen atmosphere. Stir at 80 ° C. for 3 hours. After completion of the reaction, the four-necked flask was allowed to cool at room temperature to separate the solid components. The collected solid component was sufficiently dried in an oven to obtain Compound B-9.

(Synthesis Example 15)
2- (2-hydroxyethylthio) -thioxanthen-9-one synthesized in Synthesis Example 10 into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer (5.00 g (1 .74 × 10 ⁻² mol) and 50 g of ethyl acetate were added and stirred at 80 ° C., and then 1 drop of dibutyltin was added as a catalyst. Next, a solution prepared by dissolving 1.46 g of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 10 g of ethyl acetate was added dropwise over 10 minutes, and then the mixture was stirred as it was at 70 ° C. for 1 hour in a nitrogen atmosphere. After completion of the reaction, the four-necked flask was allowed to cool at room temperature, and the precipitated solid component was separated. The collected solid component was sufficiently dried in an oven to obtain Compound R-5.

(Synthesis Example 16)
2- (2-hydroxyethylthio) -thioxanthen-9-one synthesized in Synthesis Example 10 into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer (5.00 g (1 .74 × 10 ⁻² mol) and 50 g of methyl isobutyl ketone were added and stirred at 80 ° C., and then 1 drop of dibutyltin was added as a catalyst. Next, a solution prepared by dissolving 2.28 g of dicyclohexylmethane 4,4′-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 25 g of methyl isobutyl ketone was added dropwise over 30 minutes, and then kept at 80 ° C. for 3 hours under a nitrogen atmosphere. Stir. After completion of the reaction, the four-necked flask was allowed to cool at room temperature, and the precipitated solid component was separated. The collected solid component was sufficiently dried in an oven to obtain Compound R-6.

(Synthesis Example 17)
2- (2-hydroxyethylthio) -thioxanthen-9-one synthesized in Synthesis Example 10 into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer (5.00 g (1 .74 × 10 ⁻² mol) and 50 g of methyl isobutyl ketone were added and stirred at 80 ° C., and then 1 drop of dibutyltin was added as a catalyst. Next, a solution prepared by dissolving 4.58 g (1.91 × 10 ⁻² mol) of 1,1- (bisacryloyloxymethyl) ethyl isocyanate (produced by Showa Denko KK, Karenz BEI) in 10 g of toluene was dropped over 30 minutes. Thereafter, the mixture was stirred as it was at 80 ° C. for 2 hours under a nitrogen atmosphere. After completion of the reaction, toluene was distilled off using an evaporator. To the residue, 70 g of toluene and 20 g of ethyl acetate were added and dissolved uniformly, and washed 10 times with 40 g of ultrapure water. After washing with water, the solvent was distilled off again using an evaporator to obtain Compound R-7.

The constituent materials used in Synthesis Examples 1 to 5 are shown in Table 1, the constituent materials used in Synthesis Examples 6 to 9 are shown in Table 2, the constituent materials used in Synthesis Examples 11 to 14 are shown in Table 3, and Synthesis Examples 10 and 15 are used. The constituent materials used in ˜17 are shown in Table 4, respectively.

(2) Evaluation (Experimental Examples 1-9, Comparative Experimental Examples 1-10)
Compounds B-1 to B-9 obtained in Synthesis Examples 1 to 5 and Synthesis Examples 11 to 14, Compounds R-1 to R-7 obtained in Synthesis Examples 6 to 9 and Synthesis Examples 15 to 17, 2- (2-hydroxyethylthio) -9,10-anthraquinone, 2-hydroxymethyl-9,10-anthraquinone (HMAQ), and 2- (2-hydroxyethylthio) -thioxanthene-9 obtained in Synthesis Example 10 -The molecular weight of ON, the voltage holding ratio of the liquid crystal, and the NI point drop of the liquid crystal were evaluated by the following methods.

(Molecular weight)
1) High performance liquid chromatography (HPLC) measurement About the said compound, the sample solution melt | dissolved in tetrahydrofuran (THF) was prepared, respectively, and the high performance liquid chromatography (HPLC) measurement was performed on the following measurement conditions.
(HPLC measurement conditions)
Equipment: Acquity TM UPLC H-Class system made by waters
Column: Acquity UPLC BEH C18, 2.1mmID × 100mm Particle size: 1.7μm
Mobile phase: A: Acetonitrile
B: 5 mM ammonium acetate aqueous solution
A / B = 60/40 (0-4 minutes)
95/5 (4-9 minutes)
95/5 (9-10 minutes)
Flow rate: 0.4mL / min
PDA detector: Measurement wavelength: 190-500nm, Extraction wavelength: 400nm

  Among all peaks detected at a detection wavelength of 400 nm, the peak with the highest intensity (the peak with the highest peak height) was defined as “main peak”, and the presence or absence of the main peak was confirmed. As a result, compounds B-1 to B-9, compounds R-1 to R-3, R-5 to R-7, 2- (2-hydroxyethylthio) -9,10-anthraquinone, 2-hydroxymethyl- Main peaks were detected for 9,10-anthraquinone (HMAQ) and 2- (2-hydroxyethylthio) -thioxanthen-9-one. On the other hand, no main peak was detected for compound R-4.

2) Liquid Chromatography Mass Spectrometry (LC / MS) Measurement For compounds in which the main peak was detected, the relative molecular mass corresponding to the peak apex of the detected main peak was measured by liquid chromatography mass spectrometry (LC / MS). did.
(LC / MS measurement conditions)
Equipment: Acquity TM H-Class system / SQ Detector made by waters
Column: Acquity UPLC BEH C18, 2.1mmID × 100mm Particle size: 1.7μm
Mobile phase: A: Acetonitrile
B: 5 mM ammonium acetate aqueous solution
A / B = 60/40 (0-4 minutes)
95/5 (4-9 minutes)
95/5 (9-10 minutes)
Flow rate: 0.4 mL / min Ionization: ESI (electrospray ionization), positive / negative ion measurement
PDA detector: Measurement wavelength: 190-500nm, Extraction wavelength: 400nm

(Voltage holding ratio of liquid crystal)
0.1 g of the above compound and 1 g of liquid crystal (MLC-7021-000, manufactured by Merck & Co., Inc.) were put into a vial and heated at 120 ° C. for 1 hour to obtain a liquid crystal mixture. Next, this liquid crystal mixture is taken out, poured into a glass cell (KSSZ-10 / B111M1NSS05, manufactured by EHC) in which a transparent electrode is formed in advance, a voltage of 1 V is applied, and a voltage holding ratio at 60 Hz is measured by a 6254 type measuring device. It was measured by (Toyo Technica).
The case where the voltage holding ratio was 95% or more was marked with ◎, the case where it was 90% or more and less than 95%, and the case where it was less than 90%.
A higher voltage holding ratio means that the contamination of the liquid crystal is suppressed.

(NI point drop of liquid crystal)
0.1 g of the above compound and 1 g of liquid crystal (MLC-7021-000, manufactured by Merck & Co., Inc.) were put into a vial and heated at 120 ° C. for 1 hour to obtain a liquid crystal mixture. Next, 10 mg of this liquid crystal mixture was placed in an aluminum open pan (Epolide Service), and the NI point was measured with a DTA-TG apparatus (Seiko Instruments). The measurement was performed by heating the liquid crystal mixture from 55 ° C. to 150 ° C. at a temperature rising rate of 2 ° C./min.
The case where the amount of change with respect to the NI point of the liquid crystal was less than 2 ° C. was evaluated as “◎”;

Table 5 shows the measurement results of Experimental Examples 1 to 9, and Table 6 shows the measurement results of Comparative Experimental Examples 1 to 10, respectively. As “molecular weight” in Tables 5 and 6, since no main peak was detected by HPLC measurement in compound R-4, “weight average molecular weight” was described. Since the main peak of other compounds was detected by HPLC measurement, the “relative molecular mass” (molecular weight measured by LC / MS) corresponding to the apex of the main peak was described.

  As shown in Tables 5 and 6, Compounds B-1 to B-5 in Experimental Examples 1 to 5 having an NHCO group equivalent of 350 g / eq or less are Comparative Experimental Examples 1 in which the NHCO group equivalent is more than 350 g / eq. -4 compounds R-1 to R-4, 2- (2-hydroxyethylthio) -9,10-anthraquinone of Comparative Experimental Example 5 that does not contain an NHCO group in the molecule, and 2- of Comparative Experimental Example 6 It can be seen that the voltage holding ratio of the liquid crystal is higher and the NI drop is smaller than that of hydroxymethyl-9,10-anthraquinone (HMAQ).

  Similarly, the compounds B-6 to B-9 of Experimental Examples 6 to 9 having an NHCO group equivalent of 350 g / eq or less are the compounds R-5 of Comparative Experimental Examples 7 to 9 having an NHCO group equivalent of more than 350 g / eq. It can be seen that there is less NI point depression than ~ R-7.

2. Preparation and Evaluation of Photocurable Resin Composition (Curable Compound A)
Curable compound A-1:
A methacrylic acid-modified bisphenol F type epoxy resin (95% partially methacrylic product) was synthesized by the following method.
160 g of liquid bisphenol F type epoxy resin (Epototo YDF-8170C, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 160 g / eq), 0.1 g of p-methoxyphenol as a polymerization inhibitor, 0.2 g of triethanolamine as a catalyst, And 81.7 g of methacrylic acid were charged into the flask, dried air was fed, and the mixture was reacted at 90 ° C. with reflux stirring for 5 hours. The obtained compound was washed 20 times with ultrapure water to obtain a methacrylic acid-modified bisphenol F type epoxy resin (curable resin A-1).
Kyoeisha Chemical Light Acrylate 14EG-A:
Polyethylene glycol diacrylate represented by the following formula (molecular weight 600)

(Compound B)
Compounds B-1 to B-9 obtained in Synthesis Examples 1 to 5 and Synthesis Examples 11 to 14
(Comparative compound)
Compounds R-1 to R-7 obtained in Synthesis Examples 6 to 9 and Synthesis Examples 15 to 17
2- (2-hydroxyethylthio) -9,10-anthraquinone 2-hydroxymethyl-9,10-anthraquinone (HMAQ)
2- (2-Hydroxyethylthio) -thioxanthen-9-one obtained in Synthesis Example 10

(Thermosetting compound C)
JER resin 1004 manufactured by Mitsubishi Chemical Corporation (bisphenol A type epoxy resin, epoxy equivalent 875-975 g / eq, molecular weight 1650, softening point 97 ° C.)

(Thermosetting agent D)
Nippon Kasei Co., Ltd. ADH (Adipic acid dihydrazide, melting point 177-184 ° C.)

(Other components E)
Silica particles S-100 (manufactured by Nippon Shokubai Co., Ltd.)
Fine particle polymer F351 (thermoplastic resin particles, manufactured by Aika Kogyo Co., Ltd., softening point 120 ° C., average particle diameter 0.3 μm)
KBM-403 (γ-glycidoxypropyltrimethoxysilane, silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd.

Example 1
As the curable compound A, 430 parts by mass of the curable compound A-1 synthesized above and 200 parts by mass of light acrylate 14EG-A manufactured by Kyoeisha Chemical Co., Ltd. and 10 compounds B-1 obtained in Synthesis Example 1 as the compound B were used. 50 parts by mass of jER resin 1004 manufactured by Mitsubishi Chemical Corporation as thermosetting compound C, 90 parts by mass of ADH manufactured by Nippon Kasei Co., Ltd. as thermosetting agent D, and silica produced by Nippon Shokubai Co., Ltd. as other components E Using a three-roll mill, 130 parts by mass of particle S-100, 70 parts by mass of fine polymer F351 manufactured by Aika Co., Ltd., and 20 parts by mass of silane coupling agent KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd. become a uniform liquid. The mixture was sufficiently mixed to obtain a photocurable resin composition.

(Examples 2-9, Comparative Examples 1-10)
A photocurable resin composition was obtained in the same manner as in Example 1 except that the composition shown in Table 7 or 8 was changed.

  The display characteristics of the obtained photocurable resin composition were evaluated by the following methods.

(LCD display panel display characteristics test)
A 40 mm × 45 mm glass substrate (RT-DM88-PIN, manufactured by EHC) in which a transparent electrode and an alignment film were formed in advance using a dispenser (manufactured by Musashi Engineering) with the obtained photocurable resin composition On the top, a 35 mm × 40 mm square seal pattern (cross-sectional area 3500 μm ² ) and a 38 mm × 43 mm square seal pattern were formed as the main seal.
Next, a liquid crystal material (MLC-7021-000, manufactured by Merck & Co., Inc.) corresponding to the internal volume of the panel after bonding was precisely dropped into the main seal frame using a dispenser. Next, a pair of glass substrates was bonded together under reduced pressure, and then bonded to the atmosphere. Then, after holding the two bonded glass substrates in a light shielding box for 3 minutes, the main seal was masked with a substrate coated with a square black matrix of 36 mm × 41 mm, and 3000 mJ / cm ² of visible light was emitted. The main seal was cured by irradiating the contained light (light having a wavelength of 370 to 450 nm) and further heating at 120 ° C. for 1 hour. Then, a polarizing film was affixed on both surfaces of the obtained liquid crystal cell, and the liquid crystal display panel was obtained.

  A case where the liquid crystal is aligned until the main seal of the obtained liquid crystal display panel and there is no color unevenness; ○, a case where color unevenness occurs over a range of less than 1 mm in the vicinity of the main seal; The case where color unevenness occurred over a range of 1 mm or more from the vicinity was marked as x. O or more was defined as the present invention.

(Display characteristics test when the LCD panel is energized)
A liquid crystal display panel was produced in the same manner as the liquid crystal display panel display characteristic test, and was driven with an applied voltage of 5 V using a DC power source. At that time, when there is no white unevenness in the vicinity of the main seal and the liquid crystal display function is sufficiently exerted, ○: when white unevenness occurs in the vicinity of the main seal over a range of less than 1 mm, Δ: 1 mm from the vicinity of the main seal A case where white unevenness occurred over the above range and the device was not driven normally was marked as x. O or more was defined as the present invention.

The evaluation results of Examples 1-9 are shown in Table 7; the evaluation results of Comparative Examples 1-10 are shown in Table 8.

  As shown in Tables 7 and 8, the photocurable resin compositions of Examples 1 to 9 containing Compound B having an NHCO group equivalent of 350 g / eq or less are good both when energized and when not energized. It can be seen that the display characteristics are shown.

  In contrast, the photocurable resin compositions of Comparative Examples 1 to 4 and Comparative Examples 7 to 9 containing a comparative compound having an NHCO group equivalent of more than 350 g / eq, and Comparative Examples 5 and 6 not containing an NHCO group It can be seen that all of the 10 photocurable resin compositions have inferior display characteristics. This is probably because liquid crystal contamination could not be sufficiently suppressed because the comparative compound had little or no hydrophilic NHCO group.

  The present application claims priority based on Japanese Patent Application No. 2015-131160 filed on June 30, 2015 and Japanese Patent Application No. 2016-013332 filed on January 27, 2016. All the contents described in the application specification are incorporated herein by reference.

  The present invention can provide a photocurable resin composition having high curability for visible light and capable of highly suppressing liquid crystal contamination when used as, for example, a display element sealant, particularly a liquid crystal sealant.

Claims (16)

A curable compound A having an ethylenically unsaturated double bond in the molecule;
Compound B having an anthraquinone skeleton or a thioxanthone skeleton and three or more NHCO groups in the molecule, and an NHCO group equivalent represented by the formula (I) is 350 g / eq or less,
A photocurable resin composition comprising:
NHCO group equivalent (g / eq) = molecular weight / number of NHCO groups contained in one molecule: Formula (I)   The photocurable resin composition according to claim 1, wherein the compound B has a burette skeleton or an allophanate skeleton in the molecule. The said compound B is a photocurable resin composition of Claim 1 or 2 represented by following formula (4) or Formula (5).

(In equations (4) and (5),
L ₁ each independently represents a single bond, an alkylene group having 1 to 10 carbon atoms, an alkyleneoxy group having 1 to 10 carbon atoms, an alkylenethio group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, or a carbon number. Represents an aryleneoxy group having 6 to 10 carbon atoms or an arylenethio group having 6 to 10 carbon atoms,
X represents an organic group derived from a compound having at least p isocyanate groups in the molecule;
p represents an integer of 3 to 5) The compound B further has an ethylenically unsaturated double bond in the molecule, and the curable compound A does not have an anthraquinone skeleton or a thioxanthone skeleton. Photocurable resin composition.   The photocurable resin composition as described in any one of Claims 1-4 whose content of the said compound B is 0.01-10 mass% with respect to the said curable compound A.   The photocurable resin composition according to claim 1, wherein the curable compound A further has an epoxy group in the molecule. A thermosetting compound C having an epoxy group in the molecule;
The photocurable resin composition according to any one of claims 1 to 6, further comprising a thermosetting agent D, wherein the thermosetting compound C is different from the curable compound A.   The thermosetting agent D is at least one selected from the group consisting of a dihydrazide-based thermal latent curing agent, an imidazole-based thermal latent curing agent, an amine adduct-based thermal latent curing agent, and a polyamine-based thermal latent curing agent. The photocurable resin composition according to claim 7.   The display element sealing agent which consists of a photocurable resin composition as described in any one of Claims 1-8.   The liquid-crystal sealing compound which consists of a photocurable resin composition as described in any one of Claims 1-8.   The liquid crystal sealing agent according to claim 10, which is a liquid crystal sealing agent for a liquid crystal dropping method. A step of forming a seal pattern on one substrate using the liquid crystal sealant according to claim 10 or 11,
In the uncured state of the seal pattern, dropping the liquid crystal on the other substrate that is paired with the one substrate in the region of the seal pattern;
Superimposing the one substrate and the other substrate through the seal pattern;
Curing the seal pattern;
A method for manufacturing a liquid crystal display panel, comprising:   The method of manufacturing a liquid crystal display panel according to claim 12, wherein the step of curing the seal pattern includes a step of curing the seal pattern by irradiating the seal pattern with light.   The method for manufacturing a liquid crystal display panel according to claim 13, wherein the light applied to the seal pattern includes light in a visible light region.   The method of manufacturing a liquid crystal display panel according to claim 13, wherein the step of curing the seal pattern further includes a step of heating and curing the seal pattern irradiated with light. A pair of substrates;
A frame-shaped sealing member disposed between the pair of substrates;
A liquid crystal layer filled in a space surrounded by the seal member between the pair of substrates,
The liquid crystal display panel whose said sealing member is the hardened | cured material of the liquid-crystal sealing compound of Claim 10 or 11.