KR101962082B1 - Photo-curable resin composition, display element sealing agent, liquid crystal sealing agent, liquid crystal display panel and manufacturing method thereof - Google Patents

Abstract

An object of the present invention is to provide a photo-curing resin composition which has high curability against visible light and can highly suppress liquid crystal contamination when used, for example, as a liquid crystal sealing agent. The photo-curing resin composition of the present invention comprises a curable compound A having an ethylenically unsaturated double bond in a molecule and a sensitizer having an aminobenzoyl skeleton and an NHCO group in the molecule and having an NHCO group equivalent represented by formula (I) of 300 g / B, and a polymerization initiator C (except the polymerization initiator having an aminobenzoyl skeleton in the molecule).
Equation (I): NHCO group equivalent (g / eq) = molecular weight / number of NHCO groups contained in one molecule

Description

Photo-curable resin composition, display element sealing agent, liquid crystal sealing agent, liquid crystal display panel and manufacturing method thereof

The present invention relates to a photo-curable resin composition, a display element sealing agent, a liquid crystal sealing agent, and a liquid crystal display panel and a manufacturing method thereof.

2. Description of the Related Art In recent years, display panels such as liquid crystal displays and organic EL displays have been widely used as image display panels for various electronic apparatuses including mobile phones and personal computers. For example, the liquid crystal display panel has two transparent substrates provided with electrodes on the surface thereof, a sealing member having a frame shape sandwiched therebetween, and a liquid crystal material sealed in a region surrounded by the sealing member.

The liquid crystal display panel can be manufactured by, for example, liquid crystal dropping method. (1) applying a liquid crystal sealing agent to the inner edge of a transparent substrate to form a rim for filling the liquid crystal, (2) dropping the liquid crystal in the rim, and (3) The two substrates are superimposed under high vacuum while the liquid crystal sealing agent remains in an uncured state, and (4) the liquid crystal sealing agent is cured.

As described above, in the liquid crystal dropping method, the uncured liquid crystal sealing agent and the liquid crystal material are in contact with each other to perform photo-curing or thermal curing. Therefore, it is required that the liquid crystal sealing agent not only has high curability but also can reduce the contamination of the liquid crystal material.

As the liquid crystal sealing agent used in the liquid crystal dropping method, a compound A (photo initiating compound) obtained by reacting a photopolymerizable oligomer, a dimethylamino benzoic acid and a compound containing two or more epoxy groups in a molecule, and a hydroxy thioxanthone And a compound B (visible light sensitizing compound) obtained by reacting a compound having two or more epoxy groups in a molecule with a photo-curable resin composition (for example, Patent Document 1). Further, a sealing agent for a liquid crystal display element comprising a curable resin, a thiocyanate-based polymerization initiator, and an amine-based sensitizer having an aminobenzoyl skeleton has been proposed (for example, Patent Document 2). A sealing agent for a liquid crystal display element including a compound (photopolymerization initiator) obtained by reacting a curable resin with an oxime ester and a polyfunctional isocyanate has been proposed (for example, Patent Document 3).

International Publication No. 2012/077720 Japanese Patent No. 5759638 JP-A-2014-98763

However, since the composition disclosed in Patent Document 3 contains a photopolymerization initiator having low absorbability of light in the visible light region, the curability against light in the visible light region is low. Since the compositions shown in Patent Documents 1 and 2 contain a compound having an aminobenzoyl skeleton as a photopolymerization initiator or a sensitizer, the curing property against light in the visible light region is good. However, The elution could not be suppressed sufficiently. Thus, it is desired to provide a photo-curable resin composition that has high curability against light in the visible light region and can highly suppress liquid crystal contamination.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems and provides a photo-curable resin composition which has high curability against visible light and can highly suppress liquid crystal contamination when used, for example, as a display element sealing agent, particularly as a liquid crystal sealing agent .

(1) a curing compound A having an ethylenically unsaturated double bond in a molecule, a sensitizer B having an amino benzoyl skeleton and an NHCO group in the molecule and having an NHCO group equivalent of 300 g / eq or less represented by the formula (I) Wherein the photo-curable resin composition is a photocurable resin composition.

Equation (I): NHCO group equivalent (g / eq) = molecular weight / number of NHCO groups contained in one molecule

[2] The photocurable resin composition according to [1], wherein the sensitizer B has 3 or more NHCO groups in the molecule.

[3] The photocurable resin composition according to [1] or [2], wherein the sensitizer B has a bayylet skeleton or an allophanate skeleton in the molecule.

[4] The photocurable resin composition according to any one of [1] to [3], wherein the sensitizer B is a compound represented by the following formula (4).

(In the formula (4)

X represents a single bond, an alkylene group having 1 to 10 carbon atoms, an alkyleneoxy group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an aryleneoxy group having 6 to 10 carbon atoms, or an arylene thio group having 6 to 10 carbon atoms ,

R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

Y represents an organic group derived from a compound having at least m isocyanate groups in the molecule,

and m represents an integer of 1 to 5)

[5] The photocurable resin composition according to any one of [1] to [4], wherein the content of the sensitizer B is 0.01 to 10 mass% with respect to the curable compound A.

[6] The photocurable resin composition according to any one of [1] to [5], wherein the polymerization initiator C has a thiazonato skeleton.

[7] The photo-curable 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 display element sealing agent comprising the photo-curable resin composition according to any one of [1] to [7].

[9] A liquid crystal sealing agent comprising the photo-curable resin composition according to any one of [1] to [7].

[10] A method for manufacturing a liquid crystal display device, comprising the steps of: forming a sealing pattern on one substrate using a liquid crystal sealing agent according to [9]; and forming a sealing pattern in the region of the sealing pattern, A step of depositing liquid crystal on the other substrate to be laminated, a step of superimposing the one substrate and the other substrate via the sealing pattern, and a step of curing the sealing pattern .

[11] The method of manufacturing a liquid crystal display panel according to [10], wherein the step of curing the sealing pattern includes a step of irradiating the sealing pattern with light to cure the sealing pattern.

[12] The method of manufacturing a liquid crystal display panel according to [11], wherein the light irradiating the sealing pattern includes light in a visible light region.

[13] A liquid crystal display comprising 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, Wherein the liquid crystal sealing agent is a cured product of the liquid crystal sealing agent according to [9].

According to the present invention, it is possible to provide a photo-curable resin composition which has high curability against visible light and can highly suppress liquid crystal contamination when used, for example, as a display element sealing agent, particularly as a liquid crystal sealing agent.

1. Photocurable resin composition

The photo-curable resin composition of the present invention comprises the curable compound A, the sensitizer B, and the polymerization initiator C, and may further include at least one of the thermosetting compound D, the thermosetting agent E and the other component F .

1-1. Curable compound A

The curable compound A contained in the photo-curable 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 one or two or more. The compound having a (meth) acryloyl group in the molecule may be any of monomers, oligomers or polymers. (Meth) acryloyl group means acryloyl group or methacryloyl group, and (meth) acrylate means acrylate or methacrylate.

Examples of the compound having one (meth) acryloyl group in one molecule include a (meth) acrylic acid alkyl ester such as methyl (meth) acrylate, ethyl (meth) acrylate and 2-hydroxyethyl (meth) do.

Examples of the compound having two or more (meth) acryloyl groups in one molecule include di (meth) acrylate such as polyethylene glycol, propylene glycol, and polypropylene glycol; Di (meth) acrylates of tris (2-hydroxyethyl) isocyanurate; Di (meth) acrylates of diols obtained by adding at least 4 moles of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol; Di (meth) acrylates of diols obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A; Tri or tri (meth) acrylates of triols obtained by the addition of at least 3 moles of ethylene oxide or propylene oxide to 1 mole of trimethylol propane; Di (meth) acrylates of diols obtained by adding at least 4 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A; Tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate; Trimethylol propane tri (meth) acrylate or oligomers thereof; Pentaerythritol tri (meth) acrylate or oligomers thereof; Poly (meth) acrylates of dipentaerythritol; Tris (acryloxyethyl) isocyanurate; Caprolactone modified tris (acryloxyethyl) isocyanurate; Caprolactone modified tris (methacryloxyethyl) isocyanurate; Polyacrylates or polymethacrylates of alkyl-modified dipentaerythritol; Polyacrylates or polymethacrylates of caprolactone-modified dipentaerythritol; Hydroxypivalic neopentyl glycol diacrylate or dimethacrylate; Caprolactone-modified hydroxypivalic neopentyl glycol di (meth) acrylate; Ethylene oxide modified phosphoric acid acrylate or dimethacrylate; Ethylene oxide modified alkylated phosphoric acid (meth) acrylates; Neopentyl glycol, trimethylol propane, oligo (meth) acrylate of pentaerythritol, and the like.

The curable compound A may further contain an epoxy group in the molecule. The number of epoxy groups per molecule is 1 or 2 or more. If the curable compound A has not only a (meth) acryloyl group but also an epoxy group in the molecule, the photo-curable resin composition containing it can be given photo-curability and thermosetting properties. Thereby, the curability of the cured product can be enhanced.

The compound having a (meth) acryloyl group and an epoxy group in a molecule can be, for example, a (meth) acrylate glycidyl ester obtained by reacting an epoxy compound with (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 is preferably a bifunctional epoxy compound from the viewpoint of suppressing the deterioration of the adhesiveness of the cured product of the photocurable resin composition due to excessively high crosslinking density Do. Examples of the bifunctional epoxy compound include bisphenol epoxy compounds (bisphenol A type, bisphenol F type, 2,2'-diallyl bisphenol A type, bisphenol AD type and hydrogenated bisphenol type and the like), biphenyl type epoxy compounds and naphthalene Type epoxy compounds. Among them, bisphenol A-type and bisphenol F-type bisphenol-type epoxy compounds are preferable from the viewpoint of good application properties. The bisphenol-type epoxy compound has an advantage of being excellent in coating property 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.

A compound A1 having a (meth) acryloyl group in the molecule and no epoxy group may be combined with a compound A2 having a (meth) acryloyl group and an epoxy group in the molecule. Thereby, when the photo-curing resin composition further contains an epoxy compound as the thermosetting compound D, the compatibility of the epoxy compound with the compound A1 having a (meth) acryloyl group and no epoxy group in the molecule have. Since the photo-curable resin composition contains the sensitizer B having a suitable hydrophilicity, even if the photo-curable resin composition contains the compound A1 that exhibits more hydrophobicity than the compound A2, the photo-curable resin composition can suppress the elution of the photo- have. The mass ratio of the compound A2 to the compound A1 may 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 based on the total amount of 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, for example, by gel permeation chromatography (GPC) in terms of polystyrene.

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

1-2. Increase / decrease agent B

The sensitizer B contained in the photocurable resin composition of the present invention has an aminobenzoyl skeleton and an NHCO group in the molecule.

The aminobenzoyl skeleton included in the sensitizer B is represented by the following formula (1).

R ₁ and R ₂ in the formula (1) each represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Among them, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms is more preferable, and a methyl group is more preferable.

The number of aminobenzoyl skeletons per molecule is 1 or more. The number of aminobenzoyl skeletons per molecule is preferably 2 or more and more preferably 3 or more in view of obtaining sufficient sensitivity to light in the visible light region even if the content of the sensitizer B is small.

Since the NHCO group contained in the sensitizer B exhibits a suitable hydrophilicity, the dissolution of the sensitizer B into the liquid crystal material can be preferably suppressed.

The number of NHCO groups per molecule is 1 or 2 or more. From the viewpoint of highly suppressing the elution of the sensitizer B into the liquid crystal material, the number of NHCO groups per molecule is preferably 2 or more, more preferably 3 or more. (-NHCO (N-) CONH-) or an allophanate skeleton (-NHCO (N-) COO-) from the viewpoint that it is easy to increase the number of NHCO groups per molecule. .

The sensitizer B may further have an ethylenically unsaturated double bond in the molecule. In the sensitizer B having an ethylenically unsaturated double bond in the molecule, for example, since the sensitizer B and the curing compound A can polymerize during curing, the elution of the sensitizer B into the liquid crystal material is suppressed easy.

The sensitizer B may be an addition reaction product of an aminobenzoyl compound b1 having a hydroxy group in the molecule and a compound b2 having an isocyanate group in the molecule.

The "aminobenzoyl compound b1 having a hydroxy group in the molecule" is represented by the following formula (2).

X in the formula (2) is independently a single bond, an alkylene group having 1 to 10 carbon atoms (e.g., a methylene group or an ethylene group), an alkyleneoxy group having a carbon number of 1 to 10 (e.g., Etc.), an arylene group having 6 to 10 carbon atoms, an aryleneoxy group having 6 to 10 carbon atoms (e.g., phenylenoxy group), or an arylene thio group having 6 to 10 carbon atoms (e.g., phenylene thio group). Among them, an alkylene group having 1 to 10 carbon atoms is preferable because the shift of the absorption wavelength caused by the structure of X is hard to occur and the effect of sensitization by aminobenzoyl skeleton is easily obtained.

A in the formula (2) is an integer of 1 or more, preferably 1. The substitution position of the group represented by - (CO-X-OH) is not limited, but is preferably para-substituted with respect to the amino group.

R ₁ and R ₂ in formula (2) each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Among them, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms is more preferable, and a methyl group is more preferable.

The compound represented by the formula (2) is preferably represented by the following formula (2 ').

The " compound b2 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 resulting sensitizer 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 from 2 to 4, more preferably from 2 to 3, from the viewpoint that the equivalent of the NHCO group of the sensitizer B can be easily set to a certain value or less.

(-NHCO (N-) CONH-), an allophanate skeleton (-NHCO (N-) COO (-NHCO)), a compound having two or more isocyanate groups in the molecule, -) or a yelethene skeleton, and more preferably a baullet skeleton or an allophanate skeleton. That is, the compound having two or more isocyanate groups in the molecule can be represented by, for example, the following formula (3a) or (3b).

R _{3 in the} formula (3a) and R ₄ in the 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 ₃ and R ₄ is 0 or 1 or more, preferably 2 or more. R ₃ and R ₄ preferably contain a structure represented by the following formula (α), (β) or (γ), and more preferably have a structure represented by the following formula (α) or .

(R ₅ in the formula (?) 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 can be obtained, for example, by reacting a polyisocyanate with a polyisocyanate, or a polyisocyanate with a diisocyanate, Or a urethane prepolymer having a cyanate group.

Examples of the diisocyanate to be used as a raw material of the base resin or the allophanate body include tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate An aliphatic diisocyanate having 1 to 10 carbon atoms, e.g. Alicyclic diisocyanates having 6 to 15 carbon atoms such as cyclohexylene diisocyanate, hydrogenated xylylene diisocyanate and isophorone diisocyanate; And aromatic diisocyanates such as tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, naphthalene diisocyanate, And aromatic diisocyanates having 6 to 15 carbon atoms such as naphthoic acid.

The polyisocyanate as a raw material for the urethane prepolymer is a polyfunctional aliphatic, alicyclic or aromatic isocyanate, and examples thereof include the above-mentioned diisocyanate. Examples of the polyol as a raw material for the urethane prepolymer include aliphatic polyols such as ethylene glycol, 1,3-propanediol, polyethylene glycol, dipropylene glycol and pentaerythritol; Alicyclic polyols such as 1,4-cyclohexane dimethanol, 1,4-cyclohexane diol, hydrogenated bisphenol A, and hydrogenated bisphenol F; Aromatic polyols such as bisphenol A and bisphenol F, and the like.

In addition to the addition reaction of the "aminobenzoyl compound b1 having a hydroxyl group in the molecule" and the "compound b2 having an isocyanate group in the molecule", the "hydroxyl group-containing compound b3" may be further reacted.

The " hydroxyl group-containing compound b3 " is a compound having a hydroxy group in the molecule. The hydroxy group of the hydroxyl group-containing compound b3 can be further reacted with the isocyanate group of the " compound having two or more isocyanate groups in the molecule " to form -O-CONH-. Examples of the hydroxyl group-containing compound b3 include monohydric alcohols having 1 to 20 carbon atoms such as methanol, ethanol, propanol, butanol, pentanol, hexanol and 1-octadecanol.

The hydroxyl group-containing compound b3 may further have an ethylenically unsaturated double bond. Thereby, an ethylenically unsaturated double bond can be further introduced into the sensitizer B. Examples of the hydroxyl group-containing compound b3 having an ethylenically unsaturated double bond in the molecule include (meth) acrylate substituted with a hydroxy group such as 4-hydroxybutyl acrylate.

The sensitizer B is preferably an addition reaction product of the "compound represented by the formula (2 ')" and the "compound having two or more isocyanate groups in the molecule"; It is more preferable to be an addition reaction product of the "compound represented by the formula (2 ')" and the "compound represented by the formula (3a) or (3b)".

That is, the sensitizer B is preferably a compound represented by the following formula (4).

X, R ₁ and R ₂ in the formula (4) have the same meanings as X, R ₁ and R ₂ respectively in the formula (2).

Y in the formula (4) represents a group derived from a compound having at least m isocyanate groups in the molecule. The group derived from a compound having at least m isocyanate groups in the molecule is a group derived from a compound having at least two isocyanate groups in the above-mentioned molecule and is a divalent group derived from a compound represented by the formula (3a) Is preferably a trivalent group derived from a compound represented by the formula (3b).

M in the formula (4) represents an integer of 1 to 5, preferably 2 or 3.

Examples of the sensitizer B include an addition reaction product of 3-hydroxypropyl-4- (dimethylamino) benzoate and hexamethylene diisocyanate baillet modified product, 3-hydroxypropyl-4- (dimethyl Amino) benzoate and a hexamethylene diisocyanate allophanate modified product, and compounds obtained by further reacting these compounds with octadecanol or 4-hydroxybutylacrylate.

It is also conceivable to increase the molecular weight of the sensitizer B in order to suppress the contamination of the liquid crystal material by the sensitizer B. However, simply by increasing the molecular weight of the sensitizer B, the content of the aminobenzoyl skeleton contributing to light absorption per molecule may be relatively small. As a result, it is necessary to increase the content of the sensitizer B in order to obtain a light absorptivity of a certain level or more, and the liquid crystal material may be rather contaminated. Therefore, in the present invention, it is important to set the ratio of the NHCO group contained per molecule to a certain value or more (to make the NHCO group equivalent to a certain value or less).

That is, it is preferable that the NHCO group equivalent of the sensitizer B is 300 g / eq or less. When the NHCO group equivalent of the sensitizer B is 300 g / eq or less, since the number of NHCO groups contained in the sensitizer B is relatively large, the hydrophilicity is appropriately increased, and when the photocurable resin composition is used as a liquid crystal sealing agent, The elution into the liquid crystal material can be suppressed. The NHCO group equivalent of the sensitizer B is more preferably 200 g / eq or more, more preferably 200 to 290 g / eq, and even more preferably 200 to 250 g / eq. When the NHCO group equivalent of the sensitizer B is 200 g / eq or more, the moisture resistance of the cured product of the photocurable resin composition is hardly damaged. The NHCO group equivalent of the sensitizer B is defined by the following formula (I).

Equation (I): NHCO group equivalent (g / eq) = molecular weight / number of NHCO groups contained in one molecule

The NHCO group equivalent of the sensitizer B can be confirmed by combining high performance liquid chromatography (HPLC) and liquid chromatography (LC / MS: Liquid Chromatography Mass Spectrometry) and NMR measurement or IR measurement. Specifically, measurement can be carried out in the following order.

1) High performance liquid chromatography (HPLC) measurement

A solution prepared by dissolving the photo-curable resin composition in tetrahydrofuran (THF) is centrifuged by a centrifuge to precipitate particle components such as silica particles and thermoplastic resin particles. The obtained solution is filtered with a filter to remove the particle components to obtain a sample liquid. The obtained sample liquid is subjected to high performance liquid chromatography (HPLC) measurement under the following measurement conditions.

(HPLC measurement conditions)

Device: Acquity TM UPLC H-Class system from waters

Column: Acquity UPLC BEH C18, 2.1 mm ID x 100 mm Diameter: 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: 0.4 mL / min

PDA detector: measurement wavelength: 190 to 500 nm, extraction wavelength: 305 nm

2) Liquid chromatography mass spectrometry (LC / MS) measurement

The relative molecular mass and the composition formula corresponding to the peak peak of the main peak detected by the detector having a wavelength of 305 nm characteristic to the aminobenzoyl skeleton were measured by liquid chromatography mass spectrometry (LC / MS) . The " main peak " refers to a peak having the highest intensity (peak having the highest peak) among all the peaks detected at a detection wavelength of 305 nm.

(LC / MS measurement conditions)

Device: waters made Acquity TM H-Class system / SQ Detector

Column: Acquity UPLC BEH C18, 2.1 mm ID x 100 mm Diameter: 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: 0.4 mL / min

Ionization: ESI (Electrospray ionization), positive and negative ion measurement

PDA detector: measurement wavelength: 190 to 500 nm, extraction wavelength: 305 nm

3) NMR measurement or IR measurement

Further, NMR measurement or IR measurement is performed using the sample solution. Thereby, the presence or absence of a spectrum characteristic of the NHCO group or the aminobenzoyl skeleton is confirmed to specify the chemical structure.

4) The NHCO group equivalent (g / eq) is obtained by applying the molecular weight obtained in 1) and 2) above and the number of NHCO groups obtained in 3) to the above-mentioned formula (I).

In order to bring the NHCO group equivalent of the sensitizer B within the above range, the sensitizer B is preferably an addition reaction product of the "compound represented by the formula (2 ')" and the "compound having two or more isocyanate groups in the molecule" , And "compound represented by formula (2 ')" and "compound represented by formula (3a) or (3b)".

The molecular weight of the sensitizer B is preferably 500 to 5000, for example. If the molecular weight of the sensitizer B is 500 or more, it is difficult to elute in the liquid crystal, so that liquid crystal contamination can be easily reduced. When the molecular weight of the sensitizer B is 5000 or less, compatibility with the curable compound A is hardly impaired. The molecular weight of the sensitizer B is more preferably 500 or more and 3000 or less, and still more preferably 700 or more and 1500 or less.

The molecular weight of the sensitizer B can be measured by the methods 1) and 2) in the measurement of the NHCO group equivalent described above.

The sensitizer B may be a single type or a combination of two or more types.

The content of the sensitizer B is preferably 0.01 to 10% by mass relative to the total amount of the curable compound A. When the content of the sensitizer B is 0.01 mass% or more, the polymerization initiator C can be sufficiently activated, and sufficient curability tends to be obtained. When the content of the sensitizer B is 10 mass% or less, elution into the liquid crystal material is hardly caused without impairing the curability. The content of the sensitizer B is more preferably 0.1 to 5 mass%, more preferably 0.1 to 3 mass%, and particularly preferably 0.1 mass% or less and 2 mass% or less based on the total amount of the curable compound A.

1-3. Polymerization initiator C

Polymerization initiator C is a photopolymerization initiator for curing reaction of curable compound A. However, the polymerization initiator C does not include the above-described aminobenzoyl skeleton.

The photopolymerization initiator is not particularly limited, but may be a self-cleavage type photopolymerization initiator or a hydrogen-withdrawing type photopolymerization initiator.

Examples of the self-clearing type photopolymerization initiator include alkylphenone compounds such as benzyl dimethylketal such as 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE 651) Α-aminoalkylphenones such as methyl-2-morpholino (4-thiomethylphenyl) propane-1-one (IIRGACURE 907) Acylphosphine oxide compound (e.g., 2,4,6-trimethylbenzoin diphenylphosphine oxide), a tiotanone compound (e.g., bis (? 5-2,4 Yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium and the like), acetophenone compounds (for example, diethoxy Methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2- 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2- (4-thiomethylphenyl) propane-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butanone, etc.), phenylglyoxylate compounds (such as methylphenylglyoxyester), and benzoin ether compounds (such as benzoin, benzoin methyl ether, benzoin isopropyl Ether, etc.).

Examples of the hydrogen-withdrawing photopolymerization initiator include benzophenone-based compounds (for example, benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4'-dichlorobenzophenone, Benzoyl-4'-methyl-diphenylsulfide, acrylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'- Benzophenone, etc.), thioanastane compounds (for example, 2-isopropylthioxanthone, 2,4-dimethylthiazonthone, 2,4-diethylthioxanthone, 2,4- (2-carboxymethoxythioxanthone- (polytetramethylene glycol 250) diester, etc.), anthraquinone compounds (such as 2-ethyl anthraquinone), and benzyl compounds.

Among them, it is preferable that the polymerization initiator C is a thiazolane-based compound (a compound having a thiazonato skeleton). This is for the following reasons. A polymerization initiator having an excessively strong absorption of visible light may be slightly eluted in a liquid crystal or the like and cause a display failure. On the other hand, since the thiazon-based compound has a suitable sensitivity to visible light, display failure can be prevented from occurring. On the other hand, since the thiazon-based compound alone may slightly absorb visible light, it is easy to adjust to a more appropriate sensitivity by combining sensitizer B from the viewpoint of obtaining sufficient curability.

The thioanastane compound may further have a hydrophilic functional group (NHCO group or OH group), preferably an NHCO group, from the viewpoint that elution into a liquid crystal material can be easily reduced.

The thiazolane-based compound having an NHCO group is preferably an addition reaction product of the " thiazonone compound c1 having a hydroxy group in the molecule " and the " compound c2 having an isocyanate group in the molecule ".

The "thiazonthone compound c1 having a hydroxy group in the molecule" is preferably represented by the following formula (5), more preferably represented by the following formula (5 ').

L in formulas (5) and (5 ') independently represents a single bond, an alkylene group having 1 to 10 carbon atoms, an alkyleneoxy group having 1 to 10 carbon atoms, an alkylene thio group having 1 to 10 carbon atoms, An aryleneoxy group having 6 to 10 carbon atoms or an arylene thio group having 6 to 10 carbon atoms. Among them, an alkylene thio group having from 1 to 10 carbon atoms or an arylene thio group having from 6 to 10 carbon atoms is preferred because it is easy to absorb light on the longer wavelength side.

P in the formula (5) is an integer of 1 or more, preferably 1. - (L-OH) may be bonded to any of the carbon atoms of the first to eighth carbon atoms of the thiazonato skeleton, but is preferably bonded to the carbon atom at the second or seventh position.

The " compound c2 having an isocyanate group in the molecule " is a compound having one or more isocyanate groups in the molecule and has the same meaning as the above-mentioned " compound having an isocyanate group in the molecule b2 ".

The "hydroxyl group-containing compound c3" may be further reacted in addition to the addition reaction of the "thiazonone compound c1 having a hydroxy group in the molecule" and the "compound c2 having an isocyanate group in the molecule". The "hydroxyl group-containing compound c3" has the same meaning as the aforementioned "hydroxyl group-containing compound b3".

The thiazolane-based compound having an NHCO group is preferably an addition reaction product of the "compound represented by the formula (5 ')" and the "compound having two or more isocyanate groups in the molecule".

That is, the thiazolane-based compound having an NHCO group is preferably a compound represented by the following formula (6).

L in equation (6) has the same meaning as L in equation (5).

Z in the formula (6) represents a group derived from a compound having at least n isocyanate groups in the molecule. The group derived from a compound having at least n isocyanate groups in the molecule is a group derived from a compound having at least two isocyanate groups in the above-mentioned molecule, and is a divalent group derived from the compound represented by the above formula (3a) Or a trivalent group derived from a compound represented by the formula (3b).

N in the formula (6) represents an integer of 2 or more, preferably 2 or 3.

Specific examples of the thioanthone compound having an NHCO group include an addition reaction product of 2-hydroxythiothianzone and hexamethylene diisocyanate baillet modified product, an addition reaction product of 2-hydroxy thioxanthone and hexamethylene diisocyanate An addition reaction product of a nate allophanate modified product, and a compound obtained by further reacting these compounds with octadecanol or 4-hydroxybutylacrylate.

The NHCO group equivalent of the thioanastane compound having an NHCO group is preferably 350 g / eq or less, more preferably 200 to 350 g / eq, and more preferably 230 to 330 g / eq from the viewpoint of suppressing contamination of the liquid crystal material desirable. The NHCO group equivalent of the thioanastane compound is defined by the above formula (I).

The molecular weight of the polymerization initiator C is preferably 500 to 5000, for example. If the molecular weight of the polymerization initiator C is 500 or more, it is difficult to dissolve in the liquid crystal, so that liquid crystal contamination can be easily reduced. When the molecular weight of the polymerization initiator C is 5000 or less, compatibility with the curable compound A is improved. The molecular weight of the polymerization initiator C is more preferably 500 or more and 3000 or less, and still more preferably 700 or more and 1500 or less.

The molecular weight of the polymerization initiator C is defined similarly to the molecular weight of the above-mentioned sensitizer B. The molecular weight of the polymerization initiator C can be measured in the same manner as the molecular weight of the sensitizer B.

The content of the polymerization initiator C is preferably 0.01 to 10% by mass relative to the total amount of the curable compound A. If the content of the polymerization initiator C is 0.01 mass% or more, sufficient photo-curability is likely to be obtained. If the content of the polymerization initiator C is 10% by mass or less, elution into a liquid crystal material is hardly caused and sufficient photo-curability is easily obtained. The content of the polymerization initiator C is more preferably 0.1 to 5 mass%, more preferably 0.1 to 3 mass%, and particularly preferably 0.1 mass% or less and 2 mass% or less based on the total amount of the curing compound A.

The mass ratio of the polymerization initiator C to the sensitizer B is preferably 1: 0.05 to 1: 5 as the polymerization initiator C: sensitizer B. If the content ratio of the polymerization initiator C and the sensitizer B is within the above range, sufficient curability tends to be obtained even in long wavelength light. The content ratio of the polymerization initiator C to the sensitizer B is more preferably the polymerization initiator C: sensitizer B = 1: 0.1 to 1: 2.

1-4. Thermosetting compound D

The thermosetting compound D is preferably an epoxy compound having an epoxy group in the molecule. However, the thermosetting compound D is different from the curing compound A. It is more preferable that the thermosetting compound D is an epoxy compound having no (meth) acryloyl group in the molecule. The epoxy compound may be either a monomer, an oligomer or a polymer. The epoxy compound has a low solubility and diffusibility in the liquid crystal when the photo-curing resin composition is used as a liquid crystal sealing agent, for example, to improve the display characteristics of the obtained liquid crystal panel and to increase the humidity resistance of the cured product have.

The epoxy compound may be an aromatic epoxy compound having a weight average molecular weight of 500 to 10,000, preferably 1,000 to 5,000. The weight average molecular weight of the epoxy compound can be measured in terms of polystyrene by gel permeation chromatography (GPC).

Examples of the aromatic epoxy compounds include aromatic diols such as bisphenol A, bisphenol S, bisphenol F, and bisphenol AD, and aromatic diols such as ethylene glycol, propylene glycol, alkylene glycol-modified diols, An aromatic polyglycidyl ether compound obtained by the reaction of hydrin; Novolak-type polyglycidyl ether compounds obtained by reaction of polyphenols represented by phenol or cresol and novolak resins derived from formaldehyde, polyalkenylphenol or its copolymer, and epichlorohydrin; Glycidyl ether compounds of xylylene phenol resin, and the like. Among them, cresol novolak type epoxy compounds, phenol novolak type epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, triphenol methane type epoxy compounds, triphenol ether type epoxy compounds, trisphenol type epoxy compounds, Dicyclopentadiene type epoxy compounds, diphenylether type epoxy compounds and biphenyl type epoxy compounds are preferable. The epoxy compound may be a single type or a combination of two or more types.

The epoxy compound may be liquid or solid. A solid epoxy compound is preferable in that it is easy to increase moisture resistance of the cured product. The softening point of the solid epoxy compound is preferably from 40 캜 to 150 캜.

The content of the thermosetting compound D is preferably 3 to 20% by mass with respect to the photocurable resin composition. If the content of the thermosetting compound D is 3% by mass or more, moisture resistance of the cured product of the photo-curable resin composition is easily improved. If the content of the thermosetting compound D is 20 mass% or less, excessive increase in viscosity of the photo-curable resin composition can be suppressed. The content of the thermosetting compound D in the photocurable resin composition is more preferably 3 to 15% by mass, and more preferably 5 to 15% by mass.

1-5. Thermal curing agent E

The heat curing agent E does not cure the thermosetting compound D or the curing compound A (when the curing compound A further has an epoxy group in the molecule) under ordinary storage conditions (room temperature, under visible light, etc.) ≪ / RTI > The photo-curing resin composition containing the thermosetting agent E has excellent storage stability and excellent thermosetting property. The thermosetting agent E is preferably an epoxy curing agent.

The epoxy curing agent is preferably an epoxy curing agent having a melting point of not less than 50 占 폚 and not more than 250 占 폚 although it depends on the thermosetting temperature from the viewpoint of enhancing the viscosity stability of the photocurable resin composition and not damaging the moisture resistance of the cured product. More preferably an epoxy curing agent having a temperature of 100 ° C or more and 200 ° C or less, and more preferably an epoxy curing agent having a melting point of 150 ° C or more and 200 ° C or less.

Examples of epoxy curing agents include organic acid dihydrazide-based thermal latent curing agents, imidazole-based thermal latent curing agents, amine adduct-based thermal latent curing agents, and polyamine-based thermal latent curing agents.

Examples of the organic acid dihydrazide-based thermal latent curing agent include adipic acid dihydrazide (melting point 181 캜), 1,3-bis (hydrazinocarboethyl) -5-isopropyl hydantoin (melting point 120 (Melting point: 160 占 폚), dodecane diacid hydrazide (melting point: 190 占 폚), and sebacic acid dihydrazide (melting point: 189 占 폚) ) And the like. Examples of imidazole thermal latent curing agents include 2,4-diamino-6- [2'-ethylimidazolyl- (1 ')] - ethyltriazine (melting point 215-225 ° C) and 2- (Melting point 137 to 147 占 폚), and the like. The amine adduct-based thermal latent curing agent is a thermal latent curing agent composed of an additive compound obtained by reacting an amine compound having a catalytic activity with an arbitrary compound, and examples thereof include Amicure PN-40 manufactured by Ajinomoto Fine Techno Co., (Melting point of 110 占 폚), Amicure PN-23 (melting point 100 占 폚) manufactured by Ajinomoto Fine Techno Co., Amicure PN-31 (melting point 115 占 폚) manufactured by Ajinomoto Fine Techno Co., Cure PN-H (melting point 115 캜), Amicure MY-24 (melting point 120 캜) manufactured by Ajinomoto Fine Techno Co., and Amicure MY-H (melting point 131 캜) manufactured by Ajinomoto Fine Techno Co., The polyamine-based thermal latent curing agent is a thermal latent curing agent having a polymer structure obtained by reacting an amine with an epoxy. Examples thereof include Adeka Hardener EH4339S (softening point 120 to 130 占 폚, manufactured by ADEKA) and ADEKA ADEKA HARDNER EH4357S (softening point 73 to 83 DEG C) and the like. Among them, dihydrazide-based thermal latent curing agents, imidazole-based thermal latent curing agents, amine adduct-based thermal latent curing agents and polyamine-based thermal latent curing agents are preferable. The epoxy curing agent may be a single type or a combination of two or more types.

The content of the thermosetting agent E is preferably 3 to 30% by mass, more preferably 3 to 20% by mass, and still more preferably 5 to 20% by mass with respect to the photocurable resin composition. The photo-curing resin composition containing the thermosetting agent E may be a one-part curing resin composition. The one-part curing resin composition is excellent in workability because it is not necessary to mix the curing agent with the subject.

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

1-6. Other ingredients F

1-6-1. Thermoplastic resin particles

The photo-curable resin composition of the present invention may further contain thermoplastic resin particles as required. The thermoplastic resin particles include a thermoplastic resin having a softening point temperature measured by a ring method of 50 to 120 占 폚, preferably 70 to 100 占 폚, and may have a number average particle diameter of 0.05 to 5 占 퐉, preferably 0.1 to 3 占 퐉 . The photo-curing resin composition containing such a thermoplastic resin particle can alleviate the shrinkage stress generated in the cured product. Further, by setting the number average particle diameter to be not more than the upper limit value, it is possible to prevent the coating stability from being lowered by the thermoplastic resin particles when forming a sealing member with a small line width. The number average particle size can be measured by a dry particle size distribution meter.

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

The content of the thermoplastic resin particles in the photocurable resin composition is preferably 5 to 40% by mass, more preferably 7 to 30% by mass. When the content of the thermoplastic resin particles is within the above range, the thermoplastic resin particles can preferably relax the shrinkage stress upon heat curing of the photo-curable resin composition, and it is easy to form the sealing member with a desired line width.

1-6-2. Filler

The photo-curable resin composition of the present invention may further contain a filler as required. The photo-curing resin composition containing the filler may have good viscosity and strength and linear expansion property of the cured product.

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, kaolin, Talc, glass beads, cericite, activated clay, bentonite, aluminum nitride, and silicon nitride. Among them, silicon dioxide and talc are preferable.

The filler may have a shape such as a spherical shape, a plate shape, a needle shape, or an irregular shape. When the filler is spherical, the average primary particle diameter of the filler is preferably 1.5 占 퐉 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 the 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.

The content of the filler is preferably 1 to 50% by mass with respect to the photocurable resin composition. When the content of the filler is 50 mass% or less, the coating stability of the photocurable resin composition is hardly impaired. The content of the filler is more preferably 10 to 30 mass% with respect to the photocurable resin composition.

The photo-curing resin composition of the present invention further contains additives such as a thermal radical polymerization initiator, a coupling agent such as a silane coupling agent, an ion trap agent, an ion exchanger, a leveling agent, a pigment, a dye, a plasticizer and a defoaming agent .

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

The photo-curable resin composition of the present invention may further include a spacer or the like for adjusting the gap of the liquid crystal display panel.

1-7. Physical Properties of Photocurable Resin Composition

The viscosity of the E-type viscometer of the photocurable resin composition of the present invention at 25 DEG C and 2.5 rpm is preferably 200 to 450 Pa · s, more preferably 300 to 400 Pa · s. When the viscosity is in the above range, the applicability of the photocurable resin composition by the dispenser is improved.

The photocurable resin composition of the present invention can be used, for example, as a sealing agent. The sealing agent is preferably a display element sealing agent used for encapsulating a display element such as a liquid crystal display element, an organic EL element, or an LED element. The display element sealing agent is preferably a liquid crystal sealing agent, and more preferably a liquid crystal sealing agent for a liquid crystal dropping method.

The sensitizer B contained in the photocurable resin composition of the present invention tends to activate the polymerization initiator C, so that good curability tends to be obtained. Thereby, it is possible to cure in a short time while reducing the damage caused by the light to the display element such as the liquid crystal layer. Further, since the sensitizer B contains at least a certain number of NHCO groups having hydrophilicity in the molecule, the dissolution of the sensitizer B into the liquid crystal having hydrophobicity can be highly suppressed.

2. Display element panel and manufacturing method thereof

The display element panel includes a pair of substrates, a display element disposed between the pair of substrates, and a sealing member sealing the display element. The sealing member may be a cured product of the display element sealing agent 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, and LED elements. Among them, a liquid crystal display element is preferable in that the photo-curable resin composition of the present invention can suppress liquid crystal contamination well.

That is, the liquid crystal display panel of the present invention comprises 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 frame- Layer (liquid crystal display element). The sealing member may be a cured product of the liquid crystal sealing agent of the present invention. The liquid crystal sealing agent of the present invention is composed of the photocurable resin composition of the present invention.

The pair of substrates are all transparent substrates. The material of the transparent substrate may be glass or plastic such as polycarbonate, polyethylene terephthalate, polyethersulfone and PMMA.

A matrix TFT, a color filter, a black matrix, or the like may be disposed on the surface of one of the pair of substrates. On the surface of the one substrate, an alignment film may be additionally disposed. The alignment film includes a known organic alignment agent and an inorganic alignment agent.

A liquid crystal display panel is manufactured using the liquid crystal sealing agent of the present invention. The liquid crystal display panel is generally manufactured by a liquid crystal dropping method and a liquid crystal injection method, but the liquid crystal display panel of the present invention is preferably manufactured by liquid crystal dropping method.

A method of manufacturing a liquid crystal display panel by a liquid crystal dropping method,

1) forming a sealing pattern of the liquid crystal sealing agent of the present invention on one of the substrates,

2) dropping the liquid crystal in a region surrounded by the sealing pattern of the substrate or in a region of the other substrate facing the region surrounded by the sealing pattern in a state in which the sealing pattern is not cured,

3) overlapping one substrate and the other substrate via a sealing pattern,

4) curing the sealing pattern.

2), the state in which the sealing pattern is uncured refers to a state in which the curing reaction of the liquid crystal sealing agent does not proceed to the gelation point. For this reason, in the step 2), in order to suppress the dissolution of the liquid crystal sealing agent into the liquid crystal, the sealing pattern may be irradiated or heated to be semi-cured.

4), only curing by light irradiation may be performed. However, after curing by light irradiation, curing by heating may be performed. That is, the step 4) includes a step of irradiating light to the sealing pattern to cure the sealing pattern; When the liquid crystal sealing agent further includes the above-mentioned heat curing agent E, it may further include a step of heating and curing the light-irradiated sealing pattern. By performing the curing by light irradiation, the liquid crystal sealing agent can be cured in a short time, so that dissolution into the liquid crystal can be suppressed. By combining the curing by light irradiation and the curing by heating, the damage to the liquid crystal layer due to light can be reduced as compared with 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 of the wavelength has a relatively small damage to the liquid crystal material or the driving electrode. A known light source that emits ultraviolet light or visible light can be used for irradiation of light. When irradiating 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 irradiation energy may be sufficient to cure the curable compound A. The photo-curing time depends on the composition of the liquid crystal sealing agent but is, for example, about 10 minutes.

The heat curing temperature depends on the composition of the liquid crystal sealing agent but is, for example, 120 占 폚 and the heat curing time is about 2 hours.

The liquid crystal sealing agent of the present invention is reduced in dissolution into liquid crystals. Therefore, the liquid crystal display panel having the cured product of the liquid crystal sealing agent of the present invention is less likely to be contaminated by the liquid crystal, and can have high quality display performance.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. The scope of the present invention is not limited by these examples.

1. Synthesis and evaluation of sensitizer B and comparative compounds

(Synthesis Example 1)

4.00 g (1.79 x 10 ^-2 mol) of 3-hydroxypropyl-4- (dimethylamino) benzoate and 30 g of toluene were charged into a four-necked flask equipped with a stirrer, a nitrogen gas introducing tube, a reflux condenser and a thermometer After stirring at 80 캜, one drop of dibutyltin as a catalyst was added. Subsequently, a solution obtained by dissolving 3.86 g of hexamethylene diisocyanate baillet modified product (Takenate D-165N manufactured by Mitsui Chemicals, Inc., isocyanate equivalent weight 179.5 g / eq) in 10 g of toluene was added dropwise over 15 minutes , And the mixture was stirred at 80 deg. C under nitrogen atmosphere for 4 hours. After completion of the reaction, the four-necked flask was cooled at room temperature to separate the precipitated liquid component. The recovered liquid component was sufficiently dried in an oven to obtain a compound B-1.

(Synthesis Example 2)

4.00 g (1.79 x 10 ^-2 mol) of 3-hydroxypropyl-4- (dimethylamino) benzoate and 30 g of toluene were charged into a four-necked flask equipped with a stirrer, a nitrogen gas introducing tube, a reflux condenser and a thermometer After stirring at 80 캜, one drop of dibutyltin as a catalyst was added. Subsequently, a solution prepared by dissolving 4.64 g of hexamethylene diisocyanate allophanate-modified product (Takenate D-178NL manufactured by Mitsui Chemicals, Inc., isocyanate equivalent: 216.1 g / eq) in 10 g of toluene was added dropwise over 20 minutes , And the mixture was stirred at 80 占 폚 for 3 hours under a nitrogen atmosphere. After completion of the reaction, the four-necked flask was cooled at room temperature to separate the precipitated liquid component. The recovered liquid component was sufficiently dried in an oven to obtain a compound B-2.

(Synthesis Example 3)

4.00 g (1.79 x 10 ^-2 mol) of 3-hydroxypropyl-4- (dimethylamino) benzoate and 30 g of toluene were charged into a four-necked flask equipped with a stirrer, a nitrogen gas introducing tube, a reflux condenser and a thermometer After stirring at 80 캜, one drop of dibutyltin as a catalyst was added. Subsequently, a solution obtained by dissolving 2.14 g of hexamethylene diisocyanate baillet modified product (Takenate D-165N manufactured by Mitsui Chemicals, Inc., isocyanate equivalent weight 179.5 g / eq) in 10 g of toluene was added dropwise over 15 minutes did.

After confirming disappearance of 3-hydroxypropyl-4- (dimethylamino) benzoate by thin-layer chromatography (TLC), 1.94 g (7.16 x 10 ^-3 mol) of 1-octadecanol (manufactured by Tokyo Chemical Industry Co., Ltd.) Was added dropwise thereto, and the mixture was stirred at 80 占 폚 for 2 hours under a nitrogen atmosphere. After completion of the reaction, the four-necked flask was cooled in an ice bath to separate the precipitated liquid component. The recovered liquid component was sufficiently dried in an oven to obtain a compound B-3.

(Synthesis Example 4)

(8.95 × 10 ^-3 mol) of 3-hydroxypropyl-4- (dimethylamino) benzoate and 30 g of ethyl acetate were added to a four-necked flask equipped with a stirrer, a nitrogen gas introducing tube, a reflux condenser and a thermometer After stirring at 70 ° C, one drop of dibutyltin as a catalyst was added. Subsequently, a solution obtained by dissolving 1.81 g of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 10 g of ethyl acetate was added dropwise over 10 minutes, and the mixture was directly stirred at 70 캜 for 3 hours under a nitrogen atmosphere. After completion of the reaction, the four-necked flask was cooled at room temperature to separate the precipitated liquid component. The recovered liquid component was sufficiently dried in an oven to obtain a compound R-1.

(Synthesis Example 5)

(8.95 x 10 <" ³ > mol) of 3-hydroxypropyl-4- (dimethylamino) benzoate and 8.75 x ^10-3 mol of methyl isobutyl ketone were added to a four-necked flask equipped with a stirrer, a nitrogen gas introducing tube, a reflux condenser, And the mixture was stirred at 80 DEG C, and then one drop of dibutyltin as a catalyst was added. Subsequently, a solution prepared by dissolving 2.35 g of dicyclohexylmethane-4,4'-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 10 g of methyl isobutyl ketone was added dropwise over 10 minutes, C < / RTI > for 3 hours. After completion of the reaction, the four-necked flask was cooled at room temperature to separate the precipitated liquid component. The recovered liquid component was sufficiently dried in an oven to obtain a compound R-2.

(Synthesis Example 6)

2.00 g (1.32 x 10 ^-2 mol) of 4- (dimethylamino) benzyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 50 g of toluene were added to a four-necked flask equipped with a stirrer, a nitrogen gas introducing tube, a reflux condenser and a thermometer After stirring at 90 캜, one drop of dibutyltin as a catalyst was added. Subsequently, a solution obtained by dissolving 2.84 g of hexamethylene diisocyanate baillet modified product (Takenate D-165N manufactured by Mitsui Chemicals, Inc., isocyanate equivalent weight 179.5 g / eq) in 15 g of toluene was added dropwise over 10 minutes , And the mixture was stirred at 90 占 폚 for 3 hours under a nitrogen atmosphere. After completion of the reaction, the four-necked flask was cooled at room temperature, and then filtered. The recovered filtrate was subjected to solvent distillation using an evaporator to obtain a liquid compound R-3.

(Synthesis Example 7)

2.00 g (1.32 x 10 ^-2 mol) of 4- (dimethylamino) benzyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30 g of toluene were added to a four-necked flask equipped with a stirrer, a nitrogen gas introducing tube, a reflux condenser and a thermometer After stirring at 90 캜, one drop of dibutyltin as a catalyst was added. Subsequently, a solution obtained by dissolving 3.42 g of hexamethylene diisocyanate allophanate-modified product (Takenate D-178NL manufactured by Mitsui Chemicals, Inc., isocyanate equivalent: 216.1 g / eq) in 15 g of toluene was added dropwise over 10 minutes , And the mixture was stirred at 90 占 폚 for 3 hours under a nitrogen atmosphere. After completion of the reaction, the four-necked flask was allowed to cool at room temperature and then filtered. The recovered filtrate was subjected to solvent distillation using an evaporator to obtain a liquid compound R-4.

Compound R-5: 3-Hydroxypropyl-4- (dimethylamino) benzoate

Compound R-6: 4- (dimethylamino) benzyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd., the following compound)

Compound R-7: Omnipol-ASA (manufactured by IGM Resins, the following compound)

The structures of the compounds B-1 to B-3 obtained in Synthesis Examples 1 to 3 are shown in Table 1, and the structures of the compounds R-1 to R-4 obtained in Synthesis Examples 4 to 7 are shown in Table 2.

(Experimental Examples 1 to 3, Comparative Experimental Examples 1 to 7)

1) the molecular weight of the prepared compounds B-1 to B-3 and the comparative compounds R-1 to R-7, 2) the voltage holding ratio of the liquid crystal and 3) the N-I point drop of the liquid crystal were evaluated by the following methods.

1) Molecular weight

A sample liquid prepared by dissolving the prepared compound in tetrahydrofuran (THF) was prepared and subjected to high performance liquid chromatography (HPLC) measurement under the following measurement conditions. Of the total peaks detected at the detection wavelength of 305 nm, the peak having the highest intensity (the highest peak) was regarded as the main peak.

(HPLC measurement conditions)

Device: Acquity TM UPLC H-Class system from waters

Column: Acquity UPLC BEH C18, 2.1 mm ID x 100 mm Diameter: 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: 0.4 mL / min

PDA detector: measurement wavelength: 190 to 500 nm, extraction wavelength: 305 nm

For the compound in which the main peak was detected, the relative molecular mass corresponding to the peak peak of the detected main peak was measured by liquid chromatography mass spectrometry (LC / MS).

(LC / MS measurement conditions)

Device: waters made Acquity TM H-Class system / SQ Detector

Column: Acquity UPLC BEH C18, 2.1 mm ID x 100 mm Diameter: 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: 0.4 mL / min

Ionization: ESI (Electrospray ionization), positive and negative ion measurement

PDA detector: measurement wavelength: 190 to 500 nm, extraction wavelength: 305 nm

2) Voltage maintenance ratio of liquid crystal

0.1 g of the prepared compound and 1 g of liquid crystal (MLC-7021-000, manufactured by Merck) were charged into a vial bottle and heated at 120 ° C for 1 hour to obtain a liquid crystal mixture. Subsequently, this liquid crystal mixture was taken out and injected into a glass cell (KSSZ-10 / B111M1NSS05, manufactured by EHC) in which a transparent electrode had been formed in advance, and a voltage of 1 V was applied to measure a voltage holding ratio at 60 Hz using a 6254- ).

A case where the voltage holding ratio was 95% or more was rated as?, A case where the voltage holding ratio was 90% or more and less than 95% was rated as?, And a case where the voltage holding ratio was less than 90%

3) N-I point drop of liquid crystal

0.1 g of the prepared compound and 1 g of liquid crystal (MLC-7021-000, manufactured by Merck) were charged into a vial bottle and heated at 120 ° C for 1 hour to obtain a liquid crystal mixture. Subsequently, this liquid crystal mixture was taken out, and 10 mg of the liquid crystal mixture was put into an aluminum open fan (manufactured by Epolide Service), and the N-I point was measured by a DTA-TG apparatus (manufactured by Seiko Instruments).

A case where the change amount with respect to the point N-I of the liquid crystal was less than 3 占 폚 was?, A case where the change amount was less than 5 占 폚 with?

The measurement results obtained are shown in Table 3.

As shown in Table 3, the compounds B-1 to B-3 of Experimental Examples 1 to 3 having an NHCO group equivalent of 300 g / eq or less and having an aminobenzoyl skeleton were compared with each other in such a manner that the NHCO group equivalent was more than 300 g / R-1 and R-2 of Experimental Examples 1 and 2, Compound R-4 of Comparative Experimental Example 4 having no aminobenzoyl skeleton, Compounds R-5 to R-7 of Comparative Experimental Examples 5 to 7 having no NHCO group , It can be seen that the voltage holding ratio of the liquid crystal is higher, the NI point drop is smaller, and the elution into the liquid crystal is reduced.

2. Preparation and evaluation of photocurable resin composition

(Curable compound A)

Curable compound A-1: The methacrylic acid-modified bisphenol F type epoxy resin (95% partial methacrylate) obtained in Synthesis Example 8 below,

(Synthesis Example 8)

(YDF-8170C, manufactured by Shin-Etsu 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 was put into a flask, and dry air was sent, and the mixture was reacted for 5 hours while refluxing at 90 ° C with stirring. The resulting compound was washed with ultrapure water 20 times to obtain methacrylic acid-modified bisphenol F type epoxy resin.

The obtained resin was analyzed by HPLC and NMR. As a result, it was confirmed that 95% of the epoxy groups were methacryloyl-modified methacrylic acid-modified bisphenol F type epoxy resins. As a result of GPC analysis of the obtained resin, the weight average molecular weight was 792.

Light Acrylate 14E-A manufactured by Kyoeisha Chemical Co., Ltd. Polyethylene glycol diacrylate (molecular weight: 600) represented by the following formula:

Curable Compound A-2: The acrylic acid-modified bisphenol F type epoxy resin (50% partial acrylate) obtained in Synthesis Example 9 below,

(Synthesis Example 9)

First, 175 g of a bisphenol F type epoxy resin (YDF-8170C, manufactured by Shin-Nittsu Sumikin Chemical Co., Ltd., epoxy equivalence of 160 g / eq) and 37 g of acrylic acid 0.2 g of triethanolamine as a catalyst and 0.2 g of hydroquinone monomethyl ether as a polymerization inhibitor were mixed and heated and stirred at 110 캜 for 12 hours while blowing dry air to obtain an acrylic acid modified bisphenol F type epoxy resin .

The obtained resin was washed 12 times with ultrapure water and analyzed by HPLC and NMR. As a result, it was confirmed that 50% of the epoxy groups were acryloyl-modified bisphenol F type epoxy resins. As a result of GPC analysis of the obtained resin, the weight average molecular weight was 692.

(Sensitizer B)

B-1 to B-3 of Synthesis Examples 1 to 3

(Comparative compound)

The compounds R-1 to R-4 and the compounds R-5 to R-7 of the synthetic examples 4 to 7

(Polymerization initiator C)

Omnipol-TX: manufactured by IGM Resins, 2-carboxymethoxythioxanthone- (polytetramethylene glycol 250) diester

(Thermosetting compound D)

Epoxy resin: jER 1004 manufactured by Mitsubishi Chemical Co., Ltd., softening point: 97 占 폚

(Heat curing agent E)

Adipic acid dihydrazide: ADH manufactured by Nippon Hoso Co., Ltd., melting point: 177 to 184 DEG C

(Other component F)

Silica particles: S-100 manufactured by Nippon Shokubai Co., Ltd.

Thermoplastic resin particles (F351, softening point: 120 占 폚, average particle diameter 0.3 占 퐉, manufactured by Aika Kogyo Co., Ltd.)

? -glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

(Example 1)

, 420 parts by mass of the curable compound A-1 obtained in Synthetic Example 8 as the curable compound A, 200 parts by mass of polyethylene glycol diacrylate (Light Acrylate 14EG-A, manufactured by Kyoeisha Chemical Co., Ltd.) , 10 parts by mass of the compound B-1 obtained in Synthesis Example 1, 10 parts by mass of Omnipol-TX (manufactured by IGM Resins) as the polymerization initiator C and 50 parts by mass of an epoxy resin (jER 1004 made by Mitsubishi Chemical Co., , 90 parts by mass of adipic acid dihydrazide (ADH, manufactured by Nippon Kasei Kogyo Co., Ltd.) as thermosetting agent E, and 130 parts by mass of silica particles (S-100, manufactured by Nippon Shokubai Co., Ltd.) , 70 parts by mass of F351 manufactured by Aika Kogyo Co., Ltd. as thermoplastic resin particles, and 20 parts by mass of? -Glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, So as to obtain a homogeneous solution. Thus, a photocurable water To obtain a composition.

(Examples 2 to 9 and Comparative Examples 1 to 7)

A photocurable resin composition was obtained in the same manner as in Example 1 except that the composition shown in Table 4 or 5 was changed.

The display characteristics of the obtained photo-curing resin composition were evaluated by the following methods.

(Liquid crystal display panel display characteristic test at non-power-on)

The resulting photo-curable resin composition was applied onto a 40 mm x 45 mm glass substrate (RT-DM88-PIN, manufactured by EHC) on which a transparent electrode and an alignment film had been formed in advance using a dispenser (SCHOTT MASTER: Musashi Engineering Co., Ltd.) A similar sealing pattern (a sealing pattern of a square of 38 mm x 43 mm) was formed on a sealing pattern (sectional area 3500 μm ² ) (main sealing) and on the periphery thereof.

Subsequently, a liquid crystal material (MLC-7021-000, manufactured by Merck) corresponding to the capacity in the panel after the bonding was precisely dripped into the rim of the main sealing using a dispenser. Subsequently, the glass substrates to be paired were bonded together under reduced pressure, and then the glass substrates were air-laid and kneaded. Then, the two bonded glass substrates were held in the light shielding box for 3 minutes, and then the main seal was masked with a substrate coated with a square black matrix of 36 mm x 41 mm, and light having a wavelength of 370 to 450 nm was irradiated at 3000 mJ / cm < ^{2 &} gt ;, further heated at 120 DEG C for 1 hour, and then polarizing films were attached to both sides to obtain a liquid crystal display panel.

A case where color unevenness occurs in a range of less than 1 mm in the vicinity of the main sealing edge is defined as?, A case where color unevenness occurs in the vicinity of the main sealing edge in a range of 1 mm or more from the vicinity of the main sealing edge Was evaluated as " x ".

(Liquid crystal display panel display characteristic test at the time of energization)

A liquid crystal display panel was produced in the same manner as in the liquid crystal display panel display property test described above. When this liquid crystal display panel was driven at an applied voltage of 5 V by using a direct current power source, the case where the liquid crystal display function in the vicinity of the main ceiling was exerted was rated as O, and white unevenness occurred in the range of less than 1 mm in the vicinity of the main ceiling , And the case in which white spots were generated over a range of 1 mm or more from the vicinity of the main sealing to prevent normal driving.

The evaluation result of the display characteristic test at the time of non-current conduction was & cir & and the evaluation result of the display characteristic test at the time of energization was at least DELTA. The evaluation results of Examples 1 to 9 are shown in Table 4, and the evaluation results of Comparative Examples 1 to 7 are shown in Table 5.

As shown in Table 4, the photocurable resin compositions of Examples 1 to 9 including the sensitizer B having an aminobenzoyl skeleton and an NHCO group equivalent of 300 g / eq or less exhibited good display Quot ;. < / RTI >

On the other hand, as shown in Table 5, the photo-curing resin compositions of Comparative Examples 1 and 2 containing comparative compounds having an NHCO group equivalent of more than 300 g / eq, Comparative Examples 5 and 6 containing a comparative compound having no NHCO group The photo-curable resin composition of the present invention exhibits poor display characteristics. This is presumably because liquid crystal contamination could not be sufficiently suppressed because the comparative compound had little or no hydrophilic NHCO group. Compared with Examples 1 to 3 containing compounds B-1 to B-3 having an aminobenzoyl skeleton, Comparative Examples 3 and 4 including Comparative Compounds R-3 and R-4 having no aminobenzoyl skeleton The photo-curable resin composition of the present invention exhibits poor display characteristics. This is presumably because sufficient control of the sealing compound was not achieved because the increase / decrease ability of the comparative compound was low, and the liquid crystal elution of the sealing material component could not be suppressed sufficiently.

This application claims priority based on Japanese Patent Application No. 2015-246116, filed December 17, 2015. The contents of which are incorporated herein by reference.

INDUSTRIAL APPLICABILITY The present invention can provide a photo-curable resin composition which has high curability against visible light and can highly suppress liquid crystal contamination when used, for example, as a liquid crystal sealing agent.

Claims (13)

A curable compound A having an ethylenically unsaturated double bond in the molecule,
A sensitizer B having an aminobenzoyl skeleton and an NHCO group in the molecule and having an NHCO group equivalent represented by the formula (I) of 300 g / eq or less,
And a polymerization initiator C (excluding a polymerization initiator having an aminobenzoyl skeleton in the molecule).
Equation (I): NHCO group equivalent (g / eq) = molecular weight / number of NHCO groups contained in one molecule The method according to claim 1,
Wherein the sensitizer B has 3 or more NHCO groups in the molecule. The method according to claim 1,
Wherein the sensitizer B has a bayylet skeleton or an allophanate skeleton in the molecule. The method according to claim 1,
And the sensitizer B is a compound represented by the following formula (4).

(In the formula (4)
X represents a single bond, an alkylene group having 1 to 10 carbon atoms, an alkyleneoxy group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an aryleneoxy group having 6 to 10 carbon atoms, or an arylene thio group having 6 to 10 carbon atoms ,
R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
Y represents an organic group derived from a compound having at least m isocyanate groups in the molecule,
and m represents an integer of 1 to 5) The method according to claim 1,
And the content of the sensitizer B is 0.01 to 10% by mass with respect to the curable compound A. The method according to claim 1,
Wherein the polymerization initiator C has a thioazane skeleton. The method according to claim 1,
Wherein the curable compound A further has an epoxy group in the molecule. A display element sealing agent comprising the photo-curable resin composition according to claim 1. A liquid crystal sealing agent comprising the photo-curable resin composition according to claim 1. A step of forming a sealing pattern on one of the substrates using the liquid crystal sealing agent according to claim 9,
A step of dropping liquid crystal in an area of the sealing pattern or on another substrate which is paired with the one substrate in a state in which the sealing pattern is not cured,
Overlapping the one substrate and the other substrate with the sealing pattern interposed therebetween;
And a step of curing the sealing pattern. 11. The method of claim 10,
Wherein the step of curing the sealing pattern includes a step of irradiating light to the sealing pattern to cure the sealing pattern. 12. The method of claim 11,
Wherein the light irradiating the sealing pattern includes light in a visible light region. A pair of substrates,
A sealing member having a rim shape 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,
Wherein the sealing member is the cured product of the liquid crystal sealing agent according to claim 9.