JP2002069160A - Sealing agent for liquid crystal display cell, composition for sealing agent for liquid crystal display cell and liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new sealing agent for liquid crystal cell excellent in adhesion durability, low water absorption, low moisture permeability and anti- staining of liquid crystal or the like, capable of producing a liquid crystal display element which has more high quality and high durability than before. SOLUTION: A composition for a sealing agent for liquid crystal display cell is a sealing agent for liquid crystal display element, and whose coefficient of water absorption of the curing material is 2 wt.% or less. And the composition for sealing agent for liquid crystal cell consists of (1) an epoxy resin, (2) a curing agent which comprises a polyphenol compound, a polyphenol resin and those ester compounds and (3) a curing accelerator which is at least one kind chosen from alkyl urea derivatives and pphosphozine compounds. And the liquid crystal display element which is produced by the composition for sealing agent for liquid crystal display cell of this invention retains long term storage stability under the environment of high temperature and humidity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a sealant for a liquid crystal display cell, a composition for a liquid crystal display cell sealant, a liquid crystal display element, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, liquid crystal display panels having features of light weight and thinness have been widely used as display panels of various devices including personal computers. The use environment is becoming severer, and large, uniform and high-quality liquid crystal display elements are desired.

By the way, a composition for a liquid crystal display cell sealant is a liquid crystal display cell in which a liquid crystal is sealed between a transparent glass substrate or a transparent plastic substrate on which an important transparent electrode or an alignment film is appropriately disposed as a member constituting the liquid crystal display cell. It refers to a thermosetting resin composition used to form cells sealed so that it does not leak to the outside. Further, the liquid crystal display cell sealant refers to a cured product of the liquid crystal display cell sealant composition.

As a one-part thermosetting liquid crystal display cell sealant composition, for example, a one-part thermosetting liquid crystal display cell sealant composition comprising an epoxy resin base material appropriately containing a solvent and a dihydrazide-based curing agent is used. Proposed. These composition groups satisfy the basic performances related to the sealing properties of the liquid crystal cell, that is, adhesive sealing properties under normal conditions, heat resistance, electrical insulation, non-contamination of liquid crystal, etc. There is a situation in which a high-quality and high-durability liquid crystal display cell sealant composition capable of further improving the display quality of a display element is strongly demanded. That is, in recent years, a liquid crystal display element having particularly high quality and excellent durability has been required. At the same time, from the viewpoint of ensuring the reliability of the liquid crystal display element, the emergence of a composition for a liquid crystal display cell sealant that is compatible with a method of manufacturing a liquid crystal display element by a single-wafer hot-press bonding method has been eagerly desired.

[0005] Here, high quality means that the display function is assured with high definition and no display disturbance, and that the display function is secured up to the vicinity of the seal. Further, durability means that the display element can be secured for a long period of time even in an environment where the display function is severe.

[0006]

In view of the above-mentioned social background, the problem to be solved is a sealing agent for a liquid crystal display cell which can manufacture a liquid crystal display element having higher quality and higher durability than ever before. The investigation of the physical properties that cannot be lacking
It is an object to provide a novel composition for a liquid crystal display cell sealing agent. In more detail, it is possible to manufacture a liquid crystal display panel that maintains a stable liquid crystal display element function for a long time even in a high-temperature and high-humidity environment, and not only a multi-stage heat press method but also a vacuum single-sheet type or a rigid single-sheet type. In addition to the fact that the cured product of the sealant composition, particularly the cured product of the composition for the sealant, which has a low water absorption, the free ion concentration derived from the composition is low, and the cured product is water vapor. To provide a novel composition for a liquid crystal display cell sealant which is rich in gas barrier properties (low moisture permeability), has high rigidity and high toughness, has excellent adhesive seal durability, liquid crystal non-staining property, and particularly has excellent dimensional stability.
In addition, it is an object of the present invention to provide a method for producing a liquid crystal display element using the composition for a liquid crystal display cell sealing agent. For that purpose, it is necessary to investigate physical properties essential for a highly durable liquid crystal display cell sealing agent.

[0007]

Means for Solving the Problems The present inventors have made intensive studies and found that epoxy resin, a specific curing agent, a specific curing accelerator, and, if necessary, specific rubber-like polymer fine particles, an inorganic filler, and a silane. Coupling agent, if necessary, a specific solvent, a specific high softening point acrylic polymer fine particles, a specific conductive beads, a specific gap out control agent and an epoxy resin resin composition containing a specific range respectively. As a result, the inventors have found that the above-mentioned problems can be solved, and have completed the present invention. That is, the following <1> to <21> are provided.

(1) A sealant for a liquid crystal display element comprising a cured product of a composition for a liquid crystal display cell sealant, wherein the cured product has a water absorption of 2% by mass or less. Sealant. (2) The sealant for a liquid crystal display cell according to the above (1), wherein a moisture permeability at 80 ° C. passing through a cured film having a thickness of 100 μm is 200 g / m ² · 24 hrs or less.

(3) At a ratio of 1 part by mass of the liquid crystal to 0.1 part by mass of the sealant, the specific resistance of the liquid crystal after contacting at 145 ° C. for one hour is the specific resistance of the liquid crystal before contact. The sealant for a liquid crystal display cell according to the above (1) or (2), which is 250 times or less. (4) any one of the above (1) to (3), wherein the epoxy resin is cured with a curing agent comprising at least one selected from a polyhydric phenol compound, a polyhydric phenol resin and an ester thereof. The sealant for a liquid crystal display cell according to Crab.

(5) The sealant for a liquid crystal display cell according to the above (4), wherein a curing accelerator comprising at least one selected from an alkyl urea derivative and a phosphazene compound is used. (6) (1) an epoxy resin, (2) a polyhydric phenol compound, a curing agent comprising at least one selected from polyhydric phenol resins and their esterified products, and (3) at least one selected from an alkyl urea derivative and a phosphazene compound. A composition for a liquid crystal display cell sealing agent, comprising a curing accelerator comprising a seed.

(7) (1) Epoxy resin 20 to 88.
9 parts by mass, 10 to 50 parts by mass of a curing agent composed of at least one selected from (2) polyhydric phenol compounds, polyhydric phenol resins and their esterified products, and (3) at least one selected from alkyl urea derivatives and phosphazene compounds. The composition for a liquid crystal display cell sealant according to the above (6), comprising 0.1 to 20 parts by mass of a curing accelerator comprising a seed.

(8) The liquid crystal display as described in (6) or (7) above, wherein the ionic conductivity of an aqueous solution obtained by mixing the composition with pure water having the same mass is 10 mS / m or less. A composition for a cell sealing agent. (9) The composition for a liquid crystal display cell sealant according to the above (6) or (7), wherein the cured product of the composition has a water absorption of 2% by mass or less.

(10) Thickness of cured film of composition 100 μm
80 ° C. The moisture permeability passing through the 200g / m ² · 24hrs
The composition for a liquid crystal display cell sealant according to the above (6) or (7), wherein: (11) The specific resistance of the liquid crystal after contacting at 145 ° C. for 1 hour at a ratio of 1 part by mass of the liquid crystal to 0.1 part by mass of the composition is 250 times or less the specific resistance of the liquid crystal before the contact. The composition for a liquid crystal display cell sealant according to the above (6) or (7), wherein:

(12) A rubbery polymer fine particle having a softening point temperature of 0 ° C. or less and an average primary particle size of 5 μm or less accounts for 1 to 25% by mass in the composition for a liquid crystal display cell sealant. The composition for a liquid crystal display cell sealant according to the above (6) or (7), further comprising:

(13) The curing agent is a phenol novolak resin, phenol aralkyl resin, naphthol novolak resin, naphthol aralkyl resin, alicyclic compound modified phenol novolak resin, alicyclic compound modified naphthol novolak resin, polycyclic aromatic compound modified novolak resin ,
Polyhydric phenol monomer, polyvinyl phenol, vinyl phenol copolymer, polyisopropenyl phenol,
Polyisopropenyl phenol copolymer, esterified phenol novolak resin, esterified phenol aralkyl resin, esterified naphthol novolak resin, esterified naphthol aralkyl resin, esterified alicyclic compound modified phenol novolak resin, esterified alicyclic compound modified naphthol novolak Resin, esterified polycyclic aromatic compound-modified novolak resin, esterified polyhydric phenol monomer, esterified polyvinylphenol, esterified vinylphenol copolymer, esterified polyisopropenylphenol, esterified polyisopropenylphenol copolymer The composition for a liquid crystal display cell sealant according to the above (6) or (7), which is at least one selected from the union.

(14) When the alkyl urea derivative is 3- (p-
(Chlorophenyl) -1,1-dimethylurea, 3- (o, p-dichlorophenyl) -1,1-dimethylurea, 2,4- [bis (1,1-dimethylurea)] toluene, 2,6- [bis
(6) or (7), which is at least one member selected from (1,1-dimethylurea)] toluene.
The composition for a liquid crystal display cell sealant according to the above.

(15) The composition for a liquid crystal display cell sealant according to the above (6) or (7), wherein the phosphazene compound is at least one kind represented by the following general formula (12).

[0018]

Embedded image (Wherein, R ^a to R ^f are a hydrogen atom, carbon number 1 to 1)
Represents a straight-chain, branched or cyclic alkyl group of 0, or an aryl or aralkyl group having 6 to 10 carbon atoms, all of which may be the same or different. )

(16) The conductive beads 1 to 1 are further added to 100 parts by mass of the composition according to the above (6) or (7).
A composition for a liquid crystal display cell sealant comprising 5 parts by mass. (17) A liquid crystal display device using the sealant for a liquid crystal display cell according to any one of (1) to (5). (18) A liquid crystal display element obtained by using the composition for a liquid crystal display cell sealant according to any one of (6) to (16).

(19) When manufacturing a liquid crystal display element using any of TN liquid crystal, STN liquid crystal, ferroelectric liquid crystal and antiferroelectric liquid crystal, the liquid crystal display device according to any one of (6) to (16) above. The composition for a cell sealant is printed or dispensed on the bonding seal component of a glass or plastic liquid crystal cell substrate, precured at a temperature of 50 to 120 ° C., and the other substrate is aligned and overlapped. After the alignment and temporary fixing,
A liquid crystal display cell is formed by heat-pressing at 00 ° C. and bonding the substrate to a uniform thickness in the range of 1 to 7 μm to form a liquid crystal display cell, injecting a liquid crystal material into the cell, and forming an injection hole in a photocurable liquid crystal. A method for producing a liquid crystal display element, characterized in that pores are sealed with a sealant composition or a two-part liquid crystal sealant composition.

(20) When manufacturing a liquid crystal display element using any of TN liquid crystal, STN liquid crystal, ferroelectric liquid crystal and antiferroelectric liquid crystal, the liquid crystal display device according to any one of (6) to (16) above. The composition for the cell sealant is printed or dispensed on the bonding seal component of the liquid crystal cell substrate made of glass or plastic, and after precuring at a temperature of 50 to 120 ° C., the liquid crystal is dropped so that the air is not trapped. After one substrate is overlaid, aligned and temporarily fixed, the substrate is heat-pressed at 80 to 150 ° C., and the substrate is bonded and fixed to a uniform thickness of 1 to 7 μm. And a method of manufacturing a liquid crystal display element, wherein the breathing hole is sealed with a photocurable liquid crystal sealing composition or a two-liquid type liquid crystal sealing composition.

(21) A liquid crystal display device obtained by the method of manufacturing a liquid crystal display device according to the above (19) or (20).

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The sealant for a liquid crystal display cell of the present invention is a sealant for a liquid crystal display element. (A) The sealant for a liquid crystal display cell wherein the cured product has a water absorption of 2% by mass or less. Agent. Here, the water absorption is a water absorption expressed as a weight increase rate after the liquid crystal display cell sealant is immersed in boiling water for 30 minutes.

Further, in the sealing agent for liquid crystal display cells of the present invention, in addition to the above-mentioned properties (a), (b) a water vapor permeability of 80 ° C. which passes through a thickness of 100 μm of the sealing agent for liquid crystal display cells is 2.
It is preferable to have a value of not more than 00 g / m ² · 24 hrs. The water vapor transmission rate per 100 μ is determined by the following conversion formula. Moisture permeability = measured moisture permeability x [film thickness of sample (μm) /
100]

More preferably, (c) a ratio of 1 part by mass of the liquid crystal to 0.1 part by mass of the sealant for the liquid crystal display cell is 1 part by mass.
It is desirable that the specific resistance of the liquid crystal after contacting at 45 ° C. for one hour is not more than 250 times the specific resistance of the liquid crystal before contact.

That is, the sealant for a liquid crystal display cell of the present invention has the above-mentioned property (a), and preferably has one or two properties selected from (b) and (c) simultaneously. This is a liquid crystal display cell sealant that is secured.

In the sealant for liquid crystal display cells of the present invention, it is extremely important that the water absorption after immersing the cured product in boiling water for 30 minutes is 2% by mass or less. This is because the liquid crystal display element obtained by doing so can maintain a high display quality for a long time even when used in a severe environment of high temperature and high humidity. More specifically, one of the essential properties of the liquid crystal display cell sealant that enables the production of a high-quality and highly durable liquid crystal display element is (a). Similarly, the cured product of the composition for a liquid crystal display cell sealant of the present invention preferably has the property (A).

The liquid crystal display cell sealant of the present invention preferably has a water absorption of the cured product of 30 minutes after immersion in boiling water.
It is desirable that the content be less than 7% by mass, more preferably less than 1.3% by mass, particularly preferably less than 0.6% by mass.

In addition, the sealing agent for liquid crystal display cells of the present invention, together with (a) above, is expressed in terms of (a) water vapor permeation for 24 hours under an environment of 80 ° C. and 95% relative humidity passing through a cured film having a thickness of 100 μm. 80 ° C moisture permeability is 200 g / m ² ·
More preferably, it is 24 hours or less. This is because the display quality and the response speed of the liquid crystal display element in a high-temperature and high-humidity environment can be suppressed. More preferably, the moisture permeability at 80 ° C. is 100 g / m 2.
And a ² · 24hrs or less, particularly preferably 50 g / m ²
・ 24 hrs or less.

In the sealing agent for liquid crystal display cells of the present invention, in addition to the above (A) or (A) and (B), (C) 0.1 parts by mass of the sealing agent for liquid crystal display cells is added to 0.1 part by mass of the liquid crystal. It is preferable that the specific resistance of the liquid crystal after contacting at 145 ° C. for one hour is 250 times or less the specific resistance of the liquid crystal before the contact in parts by mass. This is because long-term display reliability of the obtained liquid crystal display element can be ensured. More preferably, it is 100 times or less, further preferably 50 times or less.

In the present invention, as a sealant for a liquid crystal display cell satisfying such properties, an epoxy resin is cured with a curing agent comprising a polyhydric phenol compound, a polyhydric phenol resin and an ester thereof. In addition, it has been found that the composition is preferably cured using at least one curing accelerator selected from an alkyl urea derivative and a phosphazene compound.
By doing so, a liquid crystal display element having high quality and high durability can be manufactured.

Further, in the sealant for a liquid crystal display cell of the present invention, in addition to the above-mentioned properties (a) to (c), at least one or two selected from the following (d) to (g): It is particularly preferable that the sealing agent for a liquid crystal display cell has the above properties.

(D) The glass transition temperature (Tg) is 85 ° C. or higher. (E) The coefficient of linear expansion at 0 ° C. to 80 ° C. determined by a thermomechanical analyzer (TMA) is 9 × 10 ⁻⁵ mm / m.
m / ° C or less. (F) Shore hardness D at 20 ° C. is 70 or more. (G) The storage elastic modulus at 100 to 150 ° C. determined from dynamic viscoelasticity measurement is in the range of 1 × 10 ^{5 to} 1 × 10 ⁸ Pa. These characteristics will be described in detail.

A thermomechanical analyzer (Thermome)
It is preferable that the glass transition temperature (Tg) determined by a mechanical analyzer (TMA) is 85 ° C. or higher, so that the resulting liquid crystal display element has stable display quality for a long time in a high temperature range exceeding 60 ° C. It is preferable because the property is secured and improved. More preferably, Tg is 90 ° C. or higher, and particularly preferably, Tg is in the range of 100 to 180 ° C. When the coefficient of linear expansion from 0 ° C. to 80 ° C. determined by a thermomechanical analyzer (TMA) is 9 × 10 ⁻⁵ mm / mm / ° C. or less, the dimensional stability of the obtained liquid crystal display element and, consequently, the gap width stability. Can be secured, which is preferable. More preferably, 7 × 10 ⁻⁵ mm / mm
/ ° C., particularly preferably less than 5 × 10 ⁻⁵ mm / mm / ° C.

Further, 100 obtained from the dynamic viscoelasticity measurement was used.
Storage elastic modulus of 1 × 10 ^{5 to} 1 × 10 ⁸ P
a, and the storage elastic modulus is 1 × 10
^{When the} pressure is ⁵ Pa or more, the obtained liquid crystal display element can secure sealing rigidity when exposed to a high temperature of, for example, 60 to 80 ° C., which is preferable. When the pressure is 1 × 10 ⁸ Pa or less, the seal layer is rich in toughness, and the obtained liquid crystal display element is excellent in high durability.

In the sealing agent for liquid crystal display of the present invention,
The cured product preferably has a Shore hardness D at 20 ° C. of 70 or more. The liquid crystal display cell obtained thereby can ensure a high level of shear adhesive strength.

The properties shown in (d) to (g) above are at least selected from the epoxy resins, polyhydric phenol compounds, curing agents comprising polyhydric phenol resins and their esters, alkyl urea derivatives and phosphazene compounds. One type of curing accelerator, if necessary,
Further, it can be achieved by adding the inorganic filler and the rubber-like polymer fine particles at a different ratio.

Next, the composition for a liquid crystal display cell sealant of the present invention comprises (1) an epoxy resin and (2) at least one selected from a polyhydric phenol compound, a polyhydric phenol resin and an ester thereof. A composition for a liquid crystal display cell sealant, comprising a curing agent and (3) at least one curing accelerator selected from an alkyl urea derivative and a phosphazene compound. Further, if necessary, an inorganic filler, a silane coupling agent,
By containing rubber-like polymer fine particles, solvent, etc., it is basically a high-grade, highly durable display cell sealant composition such as primary adhesive sealability, non-contamination of liquid crystal, balance between toughness and heat resistance rigidity. In addition to the required properties, in particular, the properties relating to the cured product of the thermosetting liquid crystal display cell sealant composition, which could not be attained so far, are 2% by mass or less in water absorption, and the moisture permeability at 80 ° C. is 200 g / m ² ··· 2
High functionality of less than 4 hours is possible.

The composition for a liquid crystal display cell sealant of the present invention has a cured product having a water absorption of 2.0 minutes after immersion in boiling water for 30 minutes.
% By mass or less, preferably less than 1.7% by mass. This is because the liquid crystal display element obtained by doing so can maintain a high display quality for a long time even when used in a severe environment of high temperature and high humidity. Immersion of the cured product in boiling water 3
The water absorption after 0 minute is more preferably less than 1.3% by mass, particularly preferably less than 0.6% by mass.

Further, in the composition for a liquid crystal display cell sealant of the present invention, the cured film passes through a cured film having a thickness of 100 μm at 80 ° C. and a water vapor transmission rate of 24 hours under a 95% relative humidity environment. moisture permeability of 200g / m ² · 24
hrs or less is more preferable. By doing so, it is possible to ensure the display quality and the effect of suppressing the decrease in the response speed in a high-temperature and high-humidity environment. More preferably, the moisture permeability at 80 ° C. is 100 g / m ² · 24 hrs or less, particularly preferably 50 g / m ² · 24 hrs or less.

In the composition for a liquid crystal display cell sealant of the present invention, the ionic conductivity of an aqueous solution obtained by mixing the same mass of pure water is more preferably 10 mS / m or less. By setting the ionic conductivity to 10 mS / m or less, it is possible to secure long-term display functionality of the finally obtained liquid crystal display element. More preferably, 2 mS / m
Or less, particularly preferably 0.2 mS / m or less.

In consideration of the above requirements, the composition for a liquid crystal display cell sealant of the present invention has a ratio of 0.1 part by mass of a cured product of the composition to 1 part by mass of liquid crystal when contacted at 145 ° C. for 1 hour. The specific resistance of the liquid crystal is preferably not more than 250 times the specific resistance of the original liquid crystal (the specific resistance of the liquid crystal after treatment at 145 ° C. for one hour), and the display of the liquid crystal display element obtained by doing so is preferable. This is preferable because reliability can be secured. It is more preferably 100 times or less, most preferably 50 times or less.

In the composition for a liquid crystal display cell sealant of the present invention, the cured product thereof is further subjected to TMA (Termomechanical analysis).
er), it is preferable that the resin composition has a glass transition temperature (Tg) of 85 ° C. or higher, so that the finally obtained liquid crystal display element has a long-term high-temperature range exceeding 60 ° C. The display quality stability during the period is further secured and improved. More preferably, Tg is 90 ° C. or higher, and particularly preferably, Tg is in the range of 100 to 180 ° C.

In the composition for a liquid crystal display cell sealant of the present invention, a thermomechanical analyzer (T
MA), the coefficient of linear expansion from 0 ° C to 80 ° C is 9 × 1
When it is 0 ^-5 mm / mm / ° C. or less, the dimensional stability of the obtained liquid crystal display element and, moreover, the gap width stability can be preferably secured. It is more preferably less than 7 × 10 ⁻⁵ mm / mm / ° C., particularly preferably less than 5 × 10 ⁻⁵ mm / mm / ° C.

Further, in the composition for a liquid crystal display cell sealant of the present invention, a differential thermal peak of differential scanning calorimetry (DSC) obtained by heating 10 mg of the uncured composition at a constant rate of 5 ° C. per minute. Exothermic onset temperature obtained from the curve is 50 ° C to 130 ° C
Is preferred. When the exothermic initiation temperature is 50 ° C. or higher, viscosity stability when the obtained composition for a liquid crystal display cell sealing agent is handled at around room temperature can be ensured. Low temperature fast curing when applied to

Furthermore, in the composition for a liquid crystal display cell sealant of the present invention, a differential thermal peak of differential scanning calorimetry (DSC) obtained by heating 10 mg of the uncured composition at a constant rate of 5 ° C. per minute. It is preferable that the maximum exothermic peak temperature determined from the curve is 100 ° C to 180 ° C. When the exothermic peak temperature is 100 ° C. or higher, low-temperature rapid curing when applied to the sheet-fed hot press type adhesive heating method can be ensured, and when the temperature is lower than 180 ° C., the manufacturing conditions of the liquid crystal display element are unnecessarily severe. Can be avoided.

Furthermore, in the composition for a liquid crystal display cell sealant of the present invention, the cured product has a Shore hardness D of 20.degree.
It is highly preferred that this is the case. The liquid crystal display cell obtained by doing so can secure a high level of shear adhesive strength, which is preferable.

Furthermore, in the composition for a liquid crystal display cell sealant of the present invention, the composition obtained by measuring the dynamic viscoelasticity of the cured product was 10%.
The storage elastic modulus at 0 to 150 ° C. is 1 × 10 ^{5 to} 1 × 10 ⁸
Pa, and the storage elastic modulus is 1 ×
If the pressure is 10 ⁵ Pa or more, the obtained liquid crystal display element can secure the sealing rigidity when exposed to a high temperature of, for example, 60 to 80 ° C. Further, when the pressure is less than 1 × 10 ⁸ Pa, the sealing layer is rich in toughness, and the resulting liquid crystal display element is excellent in high durability, which is preferable.

Properties related to the composition for a liquid crystal display cell sealant, such as Tg, Shore hardness D, modulus of elasticity, and coefficient of linear expansion, include epoxy resins, polyphenol compounds, polyphenol resins and esters thereof. If necessary, an inorganic filler and rubber-like polymer microparticles are added at different ratios to a curing agent composed of at least one selected from oxides and a curing accelerator composed of at least one selected from alkyl urea derivatives and phosphazene compounds. Can be achieved by

Although not particularly limited, for example, Tg
Depends strongly on the type and amount ratio of the epoxy resin, the type and amount ratio of the above-mentioned curing agent, curing conditions and the like. The Shore hardness D strongly depends on the type and amount ratio of the epoxy resin, the type and amount ratio of the above-mentioned curing agent, curing conditions, the amount ratio of the filler and the like. The elastic modulus is the type of epoxy resin and its amount ratio and the type and amount ratio of the above-mentioned curing agent, the amount ratio of rubber,
It depends strongly on curing conditions and the like. The coefficient of linear expansion strongly depends on the amount ratio of the inorganic filler and the curing conditions. In view of the above facts, it can be achieved by selecting or determining the quantitative ratio and the curing conditions so as to be within the respective preferable ranges.

In the composition for a liquid crystal display cell sealant of the present invention, the so-called B-staged composition after heat treatment at 80 ° C. for 20 minutes when the composition is applied to a thickness of 50 μm has a 90 ° C. E-type viscosity of 5%. It is preferably in the range of 1000 Pa · s. This is preferable because it functions as a sealant that is sufficiently compatible with not only the multi-stage hot press bonding system but also various single-wafer hot press heating bonding systems that are expected to exhibit high productivity. More specifically, when the E-type viscosity at 90 ° C. of the B-staged composition exceeds 5 Pa · s, it is possible to suppress the generation of through bubbles at the time of single-wafer type hot press heat press bonding, and to be 1000 Pa · s or less. By
It is preferable because a desired gap control can be performed at the time of single-wafer hot press type heat compression bonding. It is more preferably in the range of 10 to 500 Pa · s, and particularly preferably in the range of 20 to 100 Pa · s.

In order to satisfy the above-mentioned properties, the composition for a liquid crystal display cell sealant of the present invention preferably comprises a polyhydric phenol compound, a polyhydric phenol resin and an esterified product thereof per one equivalent of an epoxy group of an epoxy resin. The active phenolic hydroxyl group and / or its ester-modified group of the curing agent is in the range of 0.5 to 1.2 equivalents, preferably 0.1 to 1.2 equivalent.
The curing agent is blended in a range of 7 to 1.1 equivalents, particularly preferably 0.85 to 1 equivalent, and at least one curing accelerator selected from an alkyl urea derivative and a phosphazene compound is added in an amount of 0 to 10 equivalents. The epoxy resin composition is desirably contained in a range of 0.1 to 20% by mass, preferably 0.1 to 10% by mass.

The most preferred composition for a liquid crystal display cell sealant of the present invention comprises a rubber-like polymer fine particle having a softening point temperature of 0 ° C. or less and an average primary particle diameter of 5 μm or less. 1 to 2 in the composition
And those containing 5% by mass. By doing so, a high-quality and highly durable liquid crystal display element can be manufactured with high yield, and economical and high productivity can be ensured. Furthermore, not only can the obtained liquid crystal display element be excellent in the balance between heat resistance and cold resistance, but also it is possible to provide a display element excellent in impact seal reliability.

More preferred embodiments of the composition for a liquid crystal display cell sealant of the present invention include (1) an epoxy resin 20
To 88.9 mass%, (2) a polyhydric phenol compound, a polyhydric phenol resin and a curing agent composed of at least one selected from esterified products thereof (hereinafter, simply referred to as polyhydric phenol curing agent) 10 to 50 mass%,
(3) At least one curing accelerator selected from alkyl urea derivatives and phosphazene compounds 0.1
(4) having a softening point temperature of 0 ° C. or less;
An epoxy resin composition containing 1 to 25% by mass of rubber-like polymer fine particles whose primary particles have an average particle size of 5 μm or less.

More preferably, it comprises (1) 20 to 83.8% by mass of an epoxy resin, (2) 10 to 45% by mass of a polyhydric phenol curing agent, and (3) at least one selected from an alkyl urea derivative and a phosphazene compound. Curing accelerator 0.1
(4) rubber-like polymer fine particles having a softening point temperature of 0 ° C. or less and an average primary particle size of 5 μm or less 1
To 15% by mass (5) Inorganic filler 5 to 45% by mass (6) Silane coupling agent 0.1 to 5% by mass.

Further, in the composition for a liquid crystal display cell sealant of the present invention, if necessary, it is further compatible with the epoxy resin (7) and has a boiling point of 1 to the extent that the function and effect are not impaired.
A solvent inert to epoxy groups in the range of 50 to 220 ° C., (8) high softening point acrylic polymer fine particles having a softening point temperature of 50 ° C. or more and primary particles having an average particle size of 2 μm or less ( Hereinafter, simply referred to as high softening point polymer fine particles), (9) a gap control agent, (1)
0) conductive beads, (11) wax, leveling agent,
A sealant composition for a liquid crystal display cell, which appropriately contains a pigment, a dye, a plasticizer, an antifoaming agent, and other additives, is also preferably included.

Hereinafter, the components of the composition for a liquid crystal display cell sealant of the present invention will be specifically described in the following order. (1) Epoxy resin The epoxy resin (1) used in the present invention is not particularly limited, and a mixture of a monofunctional epoxy resin and a polyfunctional epoxy resin or a single or a mixture of polyfunctional epoxy resins can be used. For example, one or more selected from the group of cresol novolak epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, triphenolmethane epoxy resin, and triphenolethane epoxy resin can be used. The mixture may be the same or different.

The epoxy resin preferably has a weight average of 1.7 or more epoxy groups in one molecule, more preferably has a weight average of 1.9 or more epoxy groups in one molecule, and particularly preferably has a weight average of 2 or more. An epoxy resin having not less than 0.0 and not more than 6 epoxy resins. Epoxy groups in one molecule have a weight average of 1.
Heat resistance improves by setting it as seven or more. The epoxy resin (1), when used alone or as a mixture of a plurality of types, preferably has an ionic conductivity of 10 mS / m or less, more preferably 5 mS / m, of an aqueous solution obtained by mixing with the same mass of pure water. Or less, more preferably 2 mS / m or less,
When it is particularly preferable to be within the measurement limit, transfer of free ions to the liquid crystal phase can be suppressed when the cured composition for liquid crystal display cell sealant of the present invention comes into contact with liquid crystal. When two or more different types of epoxy resins are used, the above requirements may be satisfied as an index of the total content of free ions in the mixture.

The epoxy resin (1) is prepared by boiling water
The concentration of hydrolyzable chlorine in the epoxy resin calculated from the chloride ion concentration in the water extracted for 4 hours is 300 ppm.
The following is preferred. Hydrolytic chlorine concentration is 30
When the content is 0 ppm or less, migration of chlorine ions to the liquid crystal phase can be suppressed when the composition for a liquid crystal display cell sealant of the present invention comes into contact with a liquid crystal. More preferably 100 pp
m, more preferably 50 ppm or less, and most preferably chlorine ion is within the detection limit.

When two or more epoxy resins of different types are used, the above-mentioned requirements may be satisfied as an index of the total content of free chloride ions in the mixture. The epoxy resin (1) is preferably a mixture of (1-1) an epoxy resin that is liquid at room temperature (25 ° C.) and (1-2) an epoxy resin that is solid at room temperature. And the mixture is at 0 ° C
More preferably, it becomes liquid at a temperature of from about 120 ° C. to about 120 ° C.

As the epoxy resin (1), gel permeation chromatography (hereinafter simply referred to as GP)
C), the weight average molecular weight in terms of polystyrene is preferably 7,000 or less, more preferably from 150 to 5,000, and most preferably from 350 to 3,500.

When the mass average molecular weight in terms of polystyrene measured by GPC is 7000 or less, the E-type viscosity of the composition for a liquid crystal display cell sealing agent after the B-stage is changed to 1000 P
a · s or less, which is preferable because compatibility with a sheet-fed type hot press heat bonding method can be ensured. Further, by setting the polystyrene equivalent mass average molecular weight to 150 or more,
It is preferable because the obtained cured product can have both Tg suitability and B-stage suitability. The content of the epoxy resin (1) is 20 to 88.9% by mass, and preferably 20 to 83.8% by mass in the composition for a liquid crystal display cell sealant.

In the following epoxy resin (1), in order to satisfy the above requirements, a previously known dehydrolytic chlorine reduction method and / or a purification method mainly intended for the release of free ions are used. Purified or highly purified can be used as appropriate. Known purification methods are not particularly limited, and include, for example, a water washing-solvent extraction purification method, an ultrafiltration method, and a distillation purification method.

The method for ascertaining the type and amount of the epoxy resin (1) in the composition for a liquid crystal display cell sealing agent of the present invention is not particularly limited. In general, a method is used in which a fraction is quantified by GPC and each fraction is identified and identified by NMR (nuclear magnetic resonance spectrum) or the like and quantified. Means for grasping the type and amount of the epoxy resin in the liquid crystal display cell sealant as a cured product thereof is not particularly limited, but includes, for example, an infrared absorption spectrum method and a pyrolysis-chromatographic preparative method. , A wet decomposition-chromatography preparative method, a pyrolysis gas chromatography method, a thermal decomposition-mass spectrometry method, a solid-state NMR method and the like can be appropriately combined.

<Monofunctional epoxy resin> Examples of the monofunctional epoxy resin used in the present invention include aliphatic monoglycidyl ether compounds, alicyclic monoglycidyl ether compounds, aromatic monoglycidyl ether compounds,
Aliphatic monoglycidyl ester compound, aromatic monoglycidyl ester compound, alicyclic monoglycidyl ester compound, nitrogen element-containing monoglycidyl ether compound,
Monoglycidyl propyl polysiloxane compounds, monoglycidyl alkanes and the like can be mentioned. It goes without saying that a monofunctional epoxy resin other than these may be used.

(Aliphatic monoglycidyl ether compound)
For example, an aliphatic monoglycidyl ether compound obtained by reacting a polyoxyalkylene monoalkyl ether having an alkyl group or an alkenyl group represented by an integer of 1 to 6 with epichlorohydrin, or an aliphatic alcohol And aliphatic monoglycidyl ether compounds obtained by reaction with epichlorohydrin.

Examples of the polyoxyalkylene monoalkyl ether having an alkyl group or an alkenyl group having an integer of 1 to 6 include ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, Polyethylene glycol monoalkyl ether,
Examples thereof include propylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether, tripropylene glycol monoalkyl ether, and polypropylene glycol monoalkyl ether. Examples of the aliphatic alcohols include n-butanol, isobutanol, n-octanol, 2-ethylhexyl alcohol, dimethylolpropane monoalkyl ether, methylolpropane dialkyl ether, glycerin dialkyl ether, dimethylolpropane monoalkyl ester, and trimethylolpropane. Dialkyl esters,
Glycerin dialkyl ester and the like can be mentioned.

(Alicyclic Monoglycidyl Ether Compound)
For example, an alicyclic monoglycidyl ether compound obtained by reacting an alicyclic alcohol having a saturated cyclic alkane group represented by an integer of 6 to 9 with epichlorohydrin and the like can be mentioned. Examples of the alicyclic alcohol used in the reaction include cyclohexanol.

(Aromatic monoglycidyl ether compound)
For example, an aromatic monoglycidyl ether compound obtained by the reaction of an aromatic alcohol with epichlorohydrin and the like can be mentioned. As the aromatic alcohol used in the reaction, phenol, methylphenol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, benzyl alcohol, t-
Butylphenol, xylenol, naphthol and the like.

(Aliphatic or aromatic monoglycidyl ester compound) For example, an aliphatic monoglycidyl ester compound or an aromatic monoglycidyl ester compound obtained by reacting an aliphatic dicarboxylic acid monoalkyl ester or an aromatic dicarboxylic acid monoalkyl ester with epichlorohydrin Glycidyl ester compounds and the like.

<Polyfunctional Epoxy Resin> The polyfunctional epoxy resin is usually an epoxy resin having a mass average of 2 to 6 epoxy groups in one molecule, but it is within a range not to impair the effects of the present invention. For example, a resin having more epoxy groups can be used. Examples of the polyfunctional epoxy resin include, for example, an aliphatic polyvalent glycidyl ether compound, an aromatic polyvalent glycidyl ether compound, a trisphenol type polyvalent glycidyl ether compound, a hydroquinone type polyvalent glycidyl ether compound, a resorcinol type polyvalent glycidyl ether compound, Aliphatic polyglycidyl ester compounds, aromatic polyglycidyl ester compounds, aliphatic polyglycidyl ether ester compounds, aromatic polyglycidyl ether ester compounds, alicyclic polyglycidyl ether compounds, aliphatic polyglycidylamine compounds And polyhydric aromatic glycidylamine compounds, hydantoin type polyvalent glycidyl compounds, biphenyl type polyvalent glycidyl compounds, novolak type polyvalent glycidyl ether compounds, and epoxidized diene polymers. Needless to say, other polyfunctional epoxy resins can also be used.

(Aliphatic polyvalent glycidyl ether compound)
For example, aliphatic polyhydric glycidyl ether compounds obtained by reacting polyoxyalkylene glycols or polyhydric alcohols with epichlorohydrin and the like can be mentioned. Examples of polyoxyalkylene glycols used in the reaction include, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
Tripropylene glycol, polypropylene glycol and the like. Examples of the polyhydric alcohol used for the reaction include dimethylolpropane, trimethylolpropane, spiroglycol, glycerin and the like.

(Aromatic polyvalent glycidyl ether compound)
For example, aromatic polyvalent glycidyl ether compounds obtained by the reaction of aromatic diols with epichlorohydrin and the like can be mentioned. Examples of the aromatic diol used in the reaction include bisphenol A, bisphenol S, bisphenol F, bisphenol AD and the like. (Trisphenol-type polyvalent glycidyl ether compound)
For example, a trisphenol-type polyvalent glycidyl ether compound obtained by a reaction between trisphenols and epichlorohydrin can be mentioned.

The trisphenols used in the reaction include 4,4 ', 4 "-methylidene trisphenol,
4,4 ', 4 "-methylidenetris (2-methylphenol), 4,4'-[(2-hydroxyphenyl) methylene] bis [2,3,6-trimethylphenol],
4,4 ', 4 "-ethylidene trisphenol, 4,
4 '-[(2-hydroxyphenyl) methylene] bis [2-methylphenol], 4,4'-[(2-hydroxyphenyl) ethylene] bis [2-methylphenol], 4,4 '-[(4 -Hydroxyphenyl) methylene] bis [2-methylphenol], 4,4 '-[(4
-Hydroxyphenyl) ethylene] bis [2-methylphenol], 4,4 '-[(2-hydroxyphenyl)
Methylene] bis [2,6-dimethylphenol], 4,
4 '-[(2-hydroxyphenyl) ethylene] bis [2,6-dimethylphenol],

4,4 '-[(4-hydroxyphenyl)
Methylene] bis [2,6-dimethylphenol], 4,
4 '-[(4-hydroxyphenyl) ethylene] bis [2,6-dimethylphenol], 4,4'-[(2-
(Hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4 ′-[(2-hydroxyphenyl) ethylene] bis [3,5-dimethylphenol],
4,4 '-[(3-hydroxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4,4'-
[(4-hydroxyphenyl) methylene] bis [2,
3,6-trimethylphenol], 4,4 '-[(2-
(Hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4 '-[(3-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4'-[( 4-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4 '-[1- [4-
[1- (4-hydroxyphenyl) -1-methylethyl] phenolethylidene] bisphenol], 4,
4 '-[(3,4-dihydroxyphenyl) methylene]
Bis [2-methylphenol], 4,4 '-[(3,4
-Dihydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4 '-[(3,4-dihydroxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4- [bis (3 -Cyclohexyl4-
Hydroxy-6-methylphenyl) methyl] -1,2-
Benzenediol and the like can be mentioned.

(Hydroquinone-type polyvalent glycidyl ether compound) Examples thereof include a hydroquinone-type polyvalent glycidyl ether compound obtained by reacting hydroquinone with epichlorohydrin. (Resorcinol-type polyvalent glycidyl ether compound) For example, a resorcinol-type polyvalent glycidyl ether compound obtained by reacting resorcinol with epichlorohydrin and the like can be mentioned.

(Aliphatic polyvalent glycidyl ester compound)
For example, an aliphatic polyhydric glycidyl ester compound obtained by a reaction between an aliphatic dicarboxylic acid represented by adipic acid and epichlorohydrin and the like can be mentioned. (Aromatic polyglycidyl ester compound) Examples include an aromatic polyglycidyl ester compound obtained by reacting an aromatic dicarboxylic acid with epichlorohydrin. Examples of the aromatic dicarboxylic acid used in the reaction include isophthalic acid, terephthalic acid, and pyromellitic acid.

(Aliphatic or Aromatic Polyglycidyl Ether Ester Compound) An aliphatic polyvalent glycidyl ether ester compound or an aromatic polyvalent glycidyl ether ester compound obtained by reacting a hydroxydicarboxylic acid compound with epichlorohydrin, etc. . (Alicyclic Polyglycidyl Ether Compound) Examples thereof include alicyclic polyvalent glycidyl ether compounds represented by dicyclopentadiene-type polyvalent glycidyl ether compounds.

(Aliphatic polyvalent glycidylamine compound) Examples thereof include an aliphatic polyvalent glycidylamine compound obtained by a reaction of an aliphatic diamine represented by ethylenediamine and epichlorohydrin. (Aromatic polyvalent glycidylamine compound) Examples thereof include an aromatic polyvalent glycidylamine compound obtained by a reaction of an aromatic amine represented by diaminodiphenylmethane, aniline, metaxylylenediamine and epichlorohydrin, and the like. (Hydantoin-type polyvalent glycidyl compound) Examples thereof include hydantoin-type polyvalent glycidyl compounds obtained by reacting hydantoin and its derivatives with epichlorohydrin.

(Novolak-Type Polyvalent Glycidyl Ether Compound) For example, novolak-type polyvalent glycidyl ether obtained by reacting a novolak resin derived from an aromatic alcohol represented by phenol, cresol, naphthol and the like with formaldehyde and epichlorohydrin. Ether compounds and the like. Further, for example, a modified novolak obtained by a reaction of a modified aralkyl resin obtained by bonding a phenol nucleus and / or a naphthol nucleus derived from phenol and / or naphthol with p-xylylene dichloride and a para-xylene nucleus with a methylene bond to epichlorohydrin. Typical polyvalent glycidyl ether compounds are also included. (Epoxidized diene polymer) Examples include epoxidized polybutadiene and epoxidized polyisoprene.

(2) Polyhydric phenol curing agent The polyhydric phenol curing agent (2) used in the composition for a liquid crystal display cell sealant of the present invention comprises a polyhydric phenol compound, a polyhydric phenol resin and an ester thereof. It is a curing agent. As the polyhydric phenol curing agent (2), a curing agent is used in which the ionic conductivity of an aqueous solution obtained by mixing the curing agent and 10 times by mass of pure water is 2 mS / m or less. Thereby, when the cured product of the composition for a liquid crystal display cell sealant of the present invention comes into contact with a liquid crystal, unnecessary transfer of free ions to a liquid crystal phase can be suppressed. Preferably it is 1 mS / m or less, more preferably 0.2 mS / m or less. Also,
The curing agent (2) is not particularly limited, but preferably has a softening point temperature of 30 ° C. or higher, preferably 75 ° C. or higher, more preferably 75 ° C. or higher and 180 ° C., as determined by the ring and ball method specified in JIS K7234. Select and use those that are less than. The use of a polyhydric phenol curing agent having a high softening point is preferable because the hardness, Tg, elastic modulus, and heat resistance of the obtained sealant for liquid crystal display cells can be improved. The polystyrene equivalent mass average molecular weight obtained by GPC is in the range of 300 to 10,000, preferably 5 to 10,000.
It is desirable to be in the range of 00 to 7500.

In the composition for a liquid crystal display cell sealant of the present invention, the preferred equivalent ratio of the polyhydric phenol curing agent is, as described above, 1 equivalent of the epoxy group of the epoxy resin to the active phenol of the polyhydric phenol curing agent. The content of the hydroxyl group and / or its ester-modified group is in the range of 0.5 to 1.2 equivalents, preferably in the range of 0.7 to 1.1 equivalents, and particularly preferably in the range of 0.85 to 1 equivalent. 0.5
When the equivalent weight is equal to or more than less than 1.2 equivalents, a high-quality and high-durability liquid crystal display element can be manufactured by using the obtained composition for a liquid crystal display cell sealing agent or the cured liquid crystal sealing agent for a liquid crystal display cell.

The polyhydric phenol curing agent (2) is not particularly limited, but for example, the following (2-1-
a) to (2-12-a) and / or (2-1-b) to (2-12-b). (2-1-a) phenol novolak resin (2-2-a) phenol aralkyl resin (2-3-a) naphthol novolak resin (2-4-a) naphthol aralkyl resin (2-5-a) alicyclic compound Modified phenol novolak resin (2-6-a) Alicyclic compound-modified naphthol novolak resin (2-7-a) Polycyclic aromatic compound-modified novolak resin (2-8-a) Polyhydric phenol monomer (2-9) -A) Polyvinylphenol (2-10-a) vinylphenol copolymer (2-11-a) polyisopropenylphenol (2-12-a) polyisopropenylphenol copolymer

(2-1-b) esterified phenol novolak resin (2-2-b) esterified phenol aralkyl resin (2-3-b) esterified naphthol novolak resin (2-4-b) esterified naphthol aralkyl Resin (2-5-b) Esterified alicyclic compound modified phenol novolak resin (2-6-b) Esterified alicyclic compound modified naphthol novolak resin (2-7-b) Esterified polycyclic aromatic compound modified novolak resin (2-8-b) Esterified polyhydric phenol monomer (2-9-b) Esterified polyvinyl phenol (2-10-b) Esterified vinyl phenol copolymer (2-11-b) Esterified poly Isopropenyl phenol (2-12-b) esterified polyisopropenyl phenol copolymer

As the polyhydric phenol curing agent, the aforementioned (2)
-1-a) to (2-12-a) and / or (2-1-)
b) to at least one or two or more selected from (2-12-b), preferably (2-1-a) to (2-
7-a) and / or (2-1-b) to (2-7-b)
At least one or two or more selected from More preferred polyhydric phenol curing agents include (2-1-
a) to (2-2-a) and / or (2-1-b) to (2-2-b). b) to at least one selected from (2-2-b).

(2-1-a) Phenol novolak resin and (2-1-b) Esterified novolak resin The following chemical formula (1)

[0087]

Embedded image (In the formula, A ¹ represents a hydrogen atom, an aromatic acyl group, or an aliphatic acyl group. R ¹ represents a hydrogen atom, a halogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, Represents an alkoxy group or a phenyl group represented by Formulas ^{1 to 10,} and may be the same or different.
Represents an integer of 1 to 3, and may be the same or different. The number p of repeating units is an integer in the range of 0 to 100. When p = 0, it represents a bisphenol derivative. )

The phenol novolak resin (2)
-1-a) is represented by those wherein A ^{1 in} the formula is a hydrogen atom. On the other hand, the esterified phenol novolak resin (2-1-b) refers to A in the formula represented by the chemical formula (1).
¹ is a hydrogen atom, an aromatic acyl group or an aliphatic acyl group, all of A ¹ are not hydrogen atoms, and the molar ratio of hydrogen atom / acyl group is in the range of 90/10 to 0/100. Is represented by

Phenol novolak resin (2-1-a)
Examples of preferred specific examples are not particularly limited, for example, those obtained by addition-condensation of the following phenols and formaldehyde under acidic conditions are typical,
It preferably has a softening point temperature of 50 ° C. or higher, more preferably 75 ° C. or higher, according to the ring and ball method.

Preferred examples of the phenols include:
For example, phenol, cresol, xylenol, hydroquinone, methylhydroquinone, catechol, resorcinol, ethylphenol, diethylphenol, n-
One or more selected from propylphenol, isopropylphenol, n-butylphenol, t-butylphenol, 2-ethylhexylphenol, phenylphenol and the like. More preferred are phenol and / or cresol.

Esterified phenol novolak resin (2
As a specific example of -1-b), 10 to 100 of phenolic hydroxyl groups contained in the phenol nopolak resin may be used.
Those obtained by modifying an aromatic and / or aliphatic acyl by mol% are exemplified.

In the composition for a liquid crystal display cell sealant of the present invention, the polyhydric phenol curing agent (2) contains the phenol novolak resin (2-1-a) and / or the esterified phenol novolak resin (2-1-b). ) Is preferable. As more preferred polyhydric phenol curing agents,
The mixing mass ratio of the phenol novolak resin (2-1-a) and the esterified phenol novolak resin (2-1-b) is in the range of 1:99 to 99: 1, particularly preferably 10:90 to 99: It is one that is 1.

(2-2-a) Phenol aralkyl resin and (2-2-b) its esterified phenol aralkyl resin The following chemical formula (2)

[0094]

Embedded image (In the formula, A ² represents a hydrogen atom, an aromatic acyl group, or an aliphatic acyl group. R ² represents a hydrogen atom, a halogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, Represents an alkoxy group or a phenyl group represented by Formulas 1 to 10, R ³ represents a hydrogen atom or a methyl group,
R ² and R ³ may be the same or different. m ² and m ³ each represent an integer of 1 to 3, and may be the same or different. The number q of repeating units is an integer in the range of 0 to 100. When q = 0, it represents a bisphenol derivative. )

The phenol aralkyl resin (2)
-2-a) is represented by those wherein A ^{2 in} the formula is a hydrogen atom. On the other hand, the esterified phenol aralkyl resin (2-2-b) refers to A in the formula represented by the chemical formula (2).
² is a hydrogen atom, an aromatic acyl group or an aliphatic acyl group, all of A ² are not hydrogen atoms, and the molar ratio of hydrogen atom / acyl group is in the range of 90/10 to 0/100. Is represented by

Phenol aralkyl resin (2-2-a)
As a preferable example of is not particularly limited,
For example, those derived from the following phenols and a xylylene dichloride compound or a xylylene dialkyl ether compound in the presence of a Friedel-Crafts catalyst and obtained by removing free phenol to 0.01% by mass or less under reduced pressure can be mentioned. More preferably, the phenol aralkyl resin has a softening point of 50 to 120 ° C. according to a ring and ball method.

Esterified phenol aralkyl resin (2
Preferable examples of -b) include 10 to 1 of phenolic hydroxyl groups contained in the phenol aralkyl resin.
An aromatic and / or aliphatic acylated modification of 00 mol% is exemplified.

Preferred examples of phenols include phenol, cresol, xylenol, hydroquinone, methylhydroquinone, catechol, resorcin, ethylphenol, diethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, t-butylphenol, One or more selected from 2-ethylhexylphenol, phenylphenol and the like. More preferred are phenol and / or cresol.

The xylylene dichloride compounds include, for example, 1,2-xylylene dichloride,
1,3-xylylene dichloride, 1,4-xylylene dichloride, 2-methyl-1,3-xylylene dichloride, 3-methyl-1,4-xylylene dichloride, 2,4-dimethyl-1,3- Xylylene dichloride, 2,4,5-trimethyl-1,3-xylylene dichloride, 2,3-dimethyl-1,4-xylylene dichloride, 2,3,5-trimethyl-1,4-xylylene dichloride, 2-ethyl-1,3-xylylene dichloride, 2,4-diethyl-1,3-xylylene dichloride, 2,4,5-triethyl-1,3-xylylene dichloride, 2,3-diethyl-1,2 4-xylylene dichloride, 2,3,5-triethyl-1,4-xylylene dichloride and the like.

The xylylenedialkyl ether compounds include, for example, α, α'-dimethoxy-p-xylene,
α, α′-diethoxy-p-xylene, α, α′-dimethoxy-o-xylene, α, α′-diethoxy-o-xylene, α, α′-dimethoxy-m-xylene, α, α
α'-Diethoxy-m-xylene, preferably α, α'-dimethoxy-p-xylene.

In the composition for a liquid crystal display cell sealant of the present invention, the polyhydric phenol resin is the phenol aralkyl resin (2-2-a) and / or the esterified phenol aralkyl resin (2-2-b). Is one of preferred embodiments. Among them, as the polyhydric phenol resin, those having a mixing mass ratio of (2-2-a) to (2-2-b) in the range of 1:99 to 99: 1 are preferable, and more preferably 10:99 to 99: 1. 90 to 99: 1.

(2-3-a) Naphthol novolak resin and its (2-3-b) esterified naphthol novolak resin Chemical formula (3) shown below

[0103]

Embedded image (In the formula, A ³ represents a hydrogen atom, an aromatic acyl group, or an aliphatic acyl group. R ⁴ and R ⁵ each represent a hydrogen atom, a halogen atom, a hydroxyl group, a straight-chain, branched, or cyclic group having 1 to 10 carbon atoms. Represents an alkyl group, an alkoxy group having 1 to 10 carbon atoms or a phenyl group, R ⁴ and R ⁵ may be the same or different, and m ⁴ and m ⁵ each represent an integer of 1 to 3, (The number r of repeating units is an integer in the range of 0 to 100. When r = 0, it represents a bisnaphthol derivative.)

The naphthol novolak resin (2)
-3-a) is represented by those wherein A ^{3 in} the formula is a hydrogen atom. On the other hand, the esterified naphthol novolak resin (2-3-b) refers to A in the formula represented by the chemical formula (3).
³ is a hydrogen atom, an aromatic acyl group or an aliphatic acyl group, A ³ is not all hydrogen atoms, and the molar ratio of hydrogen atom / acyl group is 90/10 to 0/100.
Are represented by those in the range.

Naphthol novolak resin (2-3-a)
Is not particularly limited, but as a preferable example,
For example, there may be mentioned those obtained by subjecting the following naphthols and formaldehyde to addition condensation under acidic conditions. More preferably, it is a naphthol novolak resin having a softening point determined by a ring and ball method of 50 ° C. or higher, more preferably 75 to 150 ° C.

Preferred examples of the naphthols include α-naphthol, β-naphthol, methylnaphthol, dimethylnaphthol, trimethylnaphthol, methylethylnaphthol, ethylnaphthol, diethylnaphthol, triethylnaphthol, methyldiethylnaphthol, n One or more of propyl naphthol, di-n-propyl naphthol, isopropyl naphthol, diisopropyl naphthol, dihydroxynaphthalene, trihydroxynaphthalene and the like, and more preferably naphthol and / or methyl naphthol.

Preferred examples of the esterified naphthol novolak resin (2-3-b) include those obtained by subjecting 10 to 100 mol% of the naphthol hydroxyl groups of the naphthol resin to aromatic and / or aliphatic acylation modification. Can be

In the composition for a liquid crystal display cell sealant of the present invention, one of the preferable embodiments is that the polyhydric phenol resin is (2-3-a) and / or (2-3-b). Among them, the mass ratio of (2-3-a) :( 2-3-b) is preferably in the range of 1:99 to 99: 1, and more preferably 90:10 to 1:99. Things.

(2-4-a) A naphthol aralkyl resin and (2-4-b) its esterified naphthol aralkyl resin The following chemical formula (4)

[0110]

Embedded image (In the formula, A ⁴ represents a hydrogen atom, an aromatic acyl group, or an aliphatic acyl group. R ⁶ and R ⁷ each represent a hydrogen atom, a halogen atom, a hydroxyl group, a linear, branched, or cyclic C 1-10 alkyl group. Represents an alkyl group, an alkoxy group having 1 to 10 carbon atoms or a phenyl group, R ⁸ represents a hydrogen atom or a methyl group, and R ⁶ , R ⁷ and R ⁸ may be the same or different. ⁶ , m ⁷ and m ⁸ each represent an integer of 1 to 3 and may be the same or different, and the number of repeating units s is an integer in the range of 0 to 100. When s = 0 Represents a bisnaphthol derivative.)

The naphthol aralkyl resin (2)
-4-a) is represented by those wherein A ^{4 in} the formula is a hydrogen atom. On the other hand, the esterified naphthol aralkyl resin (2-4-b) refers to A in the formula represented by the chemical formula (4).
⁴ is a hydrogen atom, an aromatic acyl group or an aliphatic acyl group, A ⁴ is not all hydrogen atoms, and the molar ratio of hydrogen atom / acyl group is 90/10 to 0/100.
Represented in the range.

Naphthol aralkyl resin (2-4-a)
As a preferable example of is not particularly limited,
For example, those derived from naphthols and the xylylene dichloride compound or the xylylene dialkyl ether compound in the presence of a Friedel-Crafts catalyst and free naphthol reduced to 0.01% by mass or less under reduced pressure may be mentioned.

Esterified naphthol aralkyl resin (2
Preferred examples of -4-b) include, for example, one of the naphthol hydroxyl groups contained in the naphthol aralkyl resin.
Those obtained by modifying 0 to 100 mol% with an aromatic and / or aliphatic acyl are exemplified.

Preferred examples of the naphthols include α-naphthol, β-naphthol, methylnaphthol, dimethylnaphthol, trimethylnaphthol, methylethylnaphthol, ethylnaphthol, diethylnaphthol, triethylnaphthol, methyldiethylnaphthol, n-propyl One or more of naphthol, di-n-propyl naphthol, isopropyl naphthol, diisopropyl naphthol, dihydroxynaphthalene, trihydroxynaphthalene and the like can be mentioned, and naphthol and / or methyl naphthol are more preferred.

In one embodiment of the composition for a liquid crystal display cell sealant of the present invention, the polyhydric phenol resin is preferably (2-4-a) and / or (2-4-b). Among them, those having a mass ratio of (2-4-a) :( 2-4-b) in the range of 1:99 to 99: 1, more preferably 90:10 to 1:99.

(2-5-a) An alicyclic compound-modified phenol novolak resin and (2-5-b) an esterified alicyclic compound-modified phenol novolak resin represented by the following chemical formula (5)

[0117]

Embedded image (In the formula, A ⁵ represents a hydrogen atom, an aromatic acyl group, or an aliphatic acyl group. R ⁹ represents a hydrogen atom, a halogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, number 1 represents 10 alkoxy group or a phenyl group, it may be different even in the same .m ⁹
Represents an integer of 1 to 3, and may be the same or different. X represents an aliphatic ring represented by the following chemical formula (6) [formula 8] or the following chemical formula (7) [formula 9],
The number of repeating units t is an integer in the range of 0 to 100.
Those in which t = 0 represent bisphenol derivatives. )

[0118]

Embedded image

[0119]

Embedded image

The alicyclic compound-modified phenol novolak resin (2-5-a) is represented by a compound in which A ^{5 in} the formula is represented by a hydrogen atom. On the other hand, the esterified alicyclic compound-modified phenol novolak resin (2-5-b) is represented by the chemical formula (5), wherein A ⁵ is a hydrogen atom, an aromatic acyl group, or an aliphatic acyl group. are those a ⁵ are not all hydrogen atoms, the molar ratio of hydrogen atom / acyl group is represented by those in the range of 90/10 to 0/100.

Preferable specific examples of the alicyclic compound-modified novolak resin represented by the formula (6) wherein X in the formula (5) is
For example, it is represented by one derived from a phenol and a dicyclopentadiene dichloride compound or a dicyclopentadiene dialkyl ether compound in the presence of a Friedel-Crafts catalyst, and free phenol removed under reduced pressure to 0.01% by mass or less.

Preferred examples of phenols include phenol, cresol, xylenol, hydroquinone, methylhydroquinone, catechol, resorcin, ethylphenol, diethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, t-butylphenol, and the like. One or more selected from 2-ethylhexylphenol, phenylphenol and the like. More preferred are phenol and / or cresol. Examples of the dicyclopentadiene dialkyl ether compound include dicyclopentadiene dimethyl ether, dicyclopentadiene diethyl ether, dicyclopentadiene dipropyl ether, and dicyclopentadiene methyl ethyl ether.

Preferable examples of the esterified alicyclic compound-modified novolak resin include 10 to 1 of phenolic hydroxyl groups contained in the alicyclic compound-modified novolak resin.
Those obtained by subjecting 00 mol% to aromatic and / or aliphatic acylation modification are exemplified.

Preferred specific examples of the alicyclic compound-modified novolak resin in which X in the formula (5) is represented by the formula (7) include, for example, the phenols described above in the presence of a Friedel-Crafts catalyst. Derived from a cyclohexane dichloride compound or a cyclohexyl dialkyl ether represented by cyclohexane dimethoxy ether compound and / or cyclohexane diethyl ether, if necessary, in the presence of the above-mentioned naphthols, and free phenol is 0.01% by mass or less. Typified by those removed under reduced pressure.

As a preferred specific example of the esterified alicyclic compound-modified novolak resin, 10 to 100 mol% of the phenolic hydroxyl group contained in the alicyclic compound-modified novolak resin is subjected to aromatic and / or aliphatic acylation modification. Things. In the composition for a liquid crystal display cell sealant of the present invention, (2-5-
a) and / or (2-5-b) is one of the preferred embodiments. Among them, (2-5-a): (2-5
Those having a mass ratio of -b) in the range of 1:99 to 99: 1, more preferably 90:10 to 1:99.

(2-6-a) Aliphatic compound-modified naphthol novolak resin and (2-6-b) Esterified alicyclic compound-modified naphthol novolak resin The following chemical formula (8)

[0127]

Embedded image (In the formula, A ⁶ represents an elementary atom, an aromatic acyl group, or an aliphatic acyl group. R ¹⁰ and R ¹¹ are each a hydrogen atom, a halogen atom, a hydroxyl group, a linear, branched, or cyclic C ^1-10 alkyl group. Represents an alkyl group, an alkoxy group having 1 to 10 carbon atoms or a phenyl group, and R ¹⁰ and R ¹¹ may be the same or different, and m ¹⁰ and m ¹¹ each represent an integer of 1 to 3, Z represents an aliphatic ring represented by the following chemical formula (9) [formula 11] or the following chemical formula (10) [formula 12], and the number of repeating units u is 0. And an integer in the range from 100 to 100. When u = 0, it represents a bisnaphthol derivative.)

[0128]

Embedded image

[0129]

Embedded image

The alicyclic compound-modified naphthol novolak resin (2-6-a) is represented by a compound in which A ^{6 in} the formula is a hydrogen atom. On the other hand, the esterified alicyclic compound-modified naphthol novolak resin (2-6-b) means that A ⁶ in the formula represented by the chemical formula (8) is a hydrogen atom, an aromatic acyl group, or an aliphatic acyl group, A ⁶ is not all hydrogen atoms, and the hydrogen atom / acyl group molar ratio is 9
It is represented by an object in the range of 0/10 to 0/100.

Preferred specific examples of the alicyclic compound-modified naphthol novolak resin in which Z in the formula (8) is represented by the formula (9) include, for example, the naphthols and the dicyclopentane in the presence of a Friedel Crafts catalyst. It is derived from a pentadiene dichloride compound or the above-mentioned dicyclopentadiene dialkyl ether compound, and is represented by those obtained by removing free phenol to 0.01% by mass or less under reduced pressure.

Preferred examples of the esterified alicyclic compound-modified naphthol novolak resin include 10 to 1 of phenolic hydroxyl groups contained in the alicyclic compound-modified resin.
A preferable example is one in which 00 mol% is modified by aromatic and / or aliphatic acylation.

Preferred specific examples of the alicyclic compound-modified naphthol novolak resin in which Z in the formula (8) is represented by the formula (10) include, for example, the naphthols described above in the presence of a Friedel Crafts catalyst, In the presence of the above-mentioned cyclohexane dichloride compound or the above-mentioned cyclohexane dimethoxy ether compound and / or cyclohexyl dialkyl ether represented by cyclohexane diethyl ether depending on It is typified by one that has been removed under reduced pressure up to mass%.

Preferred examples of the esterified alicyclic compound-modified naphthol novolak resin include one of the phenolic hydroxyl groups inherent in the alicyclic compound-modified resin.
Those obtained by modifying 0 to 100 mol% with an aromatic and / or aliphatic acyl are exemplified. As the polyhydric phenol resin, those in which (2-6-a) and (2-6-b) are used in combination at an arbitrary ratio are also encompassed in the present invention.
6-a): 1:99 to 9 by mass ratio of (2-6-b)
It is preferably in the range of 9: 1, more preferably 9: 1.
0:10 to 1:99.

(2-7-a) Polycyclic aromatic compound-modified novolak resin and (2-7-b) esterified polycyclic aromatic compound-modified novolak resin Polycyclic aromatic compound-modified novolak resin (2-7-a) Examples of a) include phenols in the presence of a 3- to 4-ring condensed polycyclic aromatic hydrocarbon compound derived from a light heavy oil fraction distilled from a high-pressure steam catalytic cracking plant in the petroleum industry. And formaldehyde in the presence of an acid catalyst, and is represented by a condensed polycyclic aromatic compound-modified novolak resin in which the condensed polycyclic aromatic nucleus and a phenol nucleus are randomly bonded in a three-dimensional arrangement with a methylene bond. Is done.

The esterified polycyclic aromatic compound-modified novolak resin (2-7-b) is, for example, 10 to 100% of the phenolic hydroxyl group of (2-7-a).
It is represented by an aromatic and / or aliphatic acylation-modified product in which mol% is modified.

Examples of the condensed polycyclic aromatic hydrocarbon compound having 3 or 4 rings derived from the light oil fraction include, for example, the number of aromatic carbon atoms determined by ¹³ C-NMR in the light / heavy oil / the number in the light / heavy oil. Those having an aromatic carbon fraction (fa value) represented by carbon number in the range of 0.4 to 0.95, preferably 0.7 to 0.8, and ¹ H-NMR in light and heavy oils The aromatic ring hydrogen fraction (Ha value) expressed by the number of aromatic ring hydrogens / the number of hydrogens in the light and heavy oil is 0.2 to 0.8, preferably 0.35 to 0.6. Things are typical.

As the polyhydric phenol resin, (2-7-
An embodiment in which a) and (2-7-b) are used in combination at an arbitrary ratio is also encompassed in the present invention, and in particular, (2-7-a):
The ratio by mass of (2-7-b) is preferably from 1:99 to 99: 1, more preferably from 90:10 to 1:99.

(2-8-a) Polyhydric phenol monomer and (2-8-b) esterified polyhydric phenol monomer As the polyhydric phenol monomer (2-8-a), Without limitation, for example, bisphenol A, bisphenol F, bisphenol S, bisphenol A
Representative examples include bisphenol monomers represented by D and the like and the following trisphenol monomers.

Examples of the trisphenol monomer include 4,4 ′, 4 ″ -methylidene trisphenol,
4,4 ', 4 "-methylidenetris (2-methylphenol), 4,4'-[(2-hydroxyphenyl) methylene] bis [2,3,6-trimethylphenol],
4,4 ', 4 "-ethylidene trisphenol, 4,
4 '-[(2-hydroxyphenyl) methylene] bis [2-methylphenol], 4,4'-[(2-hydroxyphenyl) ethylene] bis [2-methylphenol], 4,4 '-[(4 -Hydroxyphenyl) methylene] bis [2-methylphenol], 4,4 '-[(4
-Hydroxyphenyl) ethylene] bis [2-methylphenol], 4,4 '-[(2-hydroxyphenyl)
Methylene] bis [2,6-dimethylphenol], 4,
4 '-[(2-hydroxyphenyl) ethylene] bis [2,6-dimethylphenol],

4,4 '-[(4-hydroxyphenyl)
Methylene] bis [2,6-dimethylphenol], 4,
4 '-[(4-hydroxyphenyl) ethylene] bis [2,6-dimethylphenol], 4,4'-[(2-
(Hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4 ′-[(2-hydroxyphenyl) ethylene] bis [3,5-dimethylphenol],
4,4 '-[(3-hydroxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4,4'-
[(4-hydroxyphenyl) methylene] bis [2,
3,6-trimethylphenol], 4,4 '-[(2-
(Hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4 '-[(3-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4'-[( 4-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4 '-[1- [4-
[1- (4-hydroxyphenyl) -1-methylethyl] phenolethylidene] bisphenol], 4,
4 '-[(3,4-dihydroxyphenyl) methylene]
Bis [2-methylphenol], 4,4 '-[(3,4
-Dihydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4 '-[(3,4-dihydroxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4- [bis (3 -Cyclohexyl4-
Hydroxy-6-methylphenyl) methyl] -1,2-
Benzenediol and the like are preferred.

Particularly, (2-8-a) is preferably represented by the following chemical formula (11)

[0143]

Embedded image (Wherein, A ⁷ represents a hydrogen atom, an aromatic acyl group, or an aliphatic acyl group. R ¹² represents a hydrogen atom, an acyloxy group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms;
It represents an alkoxy group having 1 to 10 carbon atoms or a phenyl group, R ¹³ represents hydrogen or an alkyl group having 10 or less carbon atoms, and R ¹² and R ¹³ may be the same or different. Y represents hydrogen, a methyl group or an ethyl group. m ¹²
And m ¹³ each represent an integer of 1 to 3, and may be the same or different. )

Wherein A ^{7 in} the formula is represented by a hydrogen atom. On the other hand, as preferred examples of the esterified polyhydric phenol monomer, those obtained by subjecting 10 to 100 mol% of the phenolic hydroxyl groups contained in the above (2-8-a) to aromatic and / or aliphatic acylation modification are preferred. No. Particularly preferably, it is represented by the chemical formula (11), wherein A ⁷ is a hydrogen atom or an aromatic acyl group or an aliphatic acyl group, and all A ⁷ are not hydrogen atoms; 90/10 atom / acyl molar ratio
To 0/100.

As the polyhydric phenol resin, (2-8-
An embodiment in which a) and (2-80b) are used in combination at an arbitrary ratio is also encompassed in the present invention, and in particular, (2-8-a):
The ratio by mass of (2-8-b) is preferably from 1:99 to 99: 1, and more preferably from 90:10 to 1:99.

(2-9-a) Polyvinylphenol and (2-9-b) Esterified Polyvinylphenol Examples of polyvinylphenol (2-9-a) include homopolymers of p-vinylphenol. You. Although there is no particular limitation, those having a mass average molecular weight in terms of polystyrene by GPC of from 300 to 20,000 are preferable, and those having a weight average molecular weight of from 500 to 10,000 are more preferably used. The esterified polyvinyl phenol (2-9-b) is, for example,
10 to 100 of the phenolic hydroxyl group of (2-9-a)
It is represented by an aromatic and / or aliphatic acylated modification of mole%.

(2-10-a) Vinylphenol copolymer and (2-10-b) Esterified vinylphenol copolymer Specific examples of the vinylphenol copolymer (2-10-a) include: For example, it is represented by a binary copolymer or a tertiary or higher copolymer with p-vinylphenol and another vinyl monomer copolymerizable with p-vinylphenol, and is not particularly limited. Preferably, the average molecular weight is in the range of 500 to 20,000,
The thing of 0 to 10000 is more preferable.

Examples of other vinyl monomers copolymerizable with p-vinylphenol include styrene, acrylonitrile, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, and hydroxy acrylate. The esterified vinyl phenol copolymer (2-10-b) refers to the above (2)
The phenolic hydroxyl group of -10-a) is typified by an aromatic and / or aliphatic acylated modification of 10 to 100 mol%.

Specific examples of (2-11-a) polyisopropenylphenol and (2-11-b) its esterified polyisopropenylphenol polyisopropenylphenol (2-11-a) include, for example, As represented by poly-p-isopropenylphenol and the like, although not particularly limited,
300 by mass average molecular weight in terms of polystyrene by GPC
To 20,000, preferably 500 to 1
It is more preferable to select and use a substance having a 0000.
In addition, esterified polyisopropenylphenol (2-
11-b) is represented, for example, by subjecting 10 to 100 mol% of the phenolic hydroxyl group of (2-11-a) to aromatic and / or aliphatic acylation modification.

(2-12-a) Polyisopropenylphenol copolymer and (2-12-b) Esterified polyisopropenylphenol copolymer Polyisopropenylphenol copolymer (2-12-a)
Specific examples of a) are represented by, for example, a binary copolymer or a tertiary copolymer of poly-p-isopropenylphenol and another vinyl monomer copolymerizable with GPC.
500 to 2 in terms of mass average molecular weight in terms of polystyrene according to
0000 is preferable, and 500 to 10
000 is more preferred.

Other vinyl monomers copolymerizable with p-isopropenylphenol include, for example, styrene,
Examples include acrylonitrile, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, and hydroxy acrylate. Further, an esterified isopropenylphenol copolymer (2-12
-B) is represented by a compound obtained by subjecting 10 to 100 mol% of the phenolic hydroxyl group of (2-12-a) to aromatic and / or aliphatic acylation modification.

In the present invention, the polyhydric phenol curing agent (2)
Other than the above, for example, a novolak resin derived from bisphenols represented by bisphenol A, bisphenol F and bisphenol S, 4,4′-
Novolak resins derived from biphenylphenols represented by biphenylphenol and the like, 1,1-di-4
Novolak resins derived from phenols having a fluorene skeleton represented by -hydroxyphenylfluorene and the like can also be used.

Most preferred polyhydric phenol curing agent (2)
Is one or more selected from phenol novolak resins, phenol aralkyl resins, esterified phenol novolak resins, and esterified phenol aralkyl resins. The polyhydric phenol curing agent (2) is an epoxy for a liquid crystal display cell sealing agent comprising an epoxy resin, a polyhydric phenol curing agent, and a curing accelerator comprising at least one selected from an alkyl urea derivative and a phosphazene compound. The ratio in the resin composition is not particularly limited, but may be 10%.
It is preferably in the range of 65 to 65% by mass. When the content is 10% by mass or more, the balance between the storage stability and the thermosetting property of the epoxy resin composition is good, and a highly durable liquid crystal display device can be manufactured. Further, the content is preferably 65% by mass or less, because it is possible to suppress the remaining of the unreacted material of the curing agent, and it is possible to maintain the crosslinking density of the cured product and the seal adhesion reliability in a good condition.

[0154] Further, 10
In order to make the ionic conductivity of the aqueous extraction solution extracted with twice the mass of pure water at 40 ° C. to 80 ° C. 2 mS / m or less, the polyhydric phenol curing agent is prepared in advance by a deionization purification method. It is desirable to use it, and the deionization purification method is, for example, free ion water extraction separation purification method, solvent extraction purification method, ultrafiltration purification method, etc., and there is no particular limitation. By the way, as the esterifying agent used when esterifying the phenolic hydroxyl group or the naphtholic hydroxyl group as described above (hereinafter, the phenolic hydroxyl group and the naphtholic hydroxyl group may be simply collectively referred to as a phenolic hydroxyl group). Any of organic carboxylic acid anhydrides, organic carboxylic acid halides, and organic carboxylic acids may be selected according to the characteristics of the esterifying agent depending on the carbon number of the ester to be derived.

Specific examples of the esterifying agent include acetic anhydride, acetyl chloride, acetyl bromide, acetic acid, propionic anhydride, propionic chloride, propionic bromide, propionic acid, butyric anhydride, butyric chloride, butyric acid, and acetic anhydride. Valeric acid, valeric acid chloride, valeric acid bromide, valeric acid, pivalic acid chloride, pivalic acid, phenylacetic acid, phenylacetic acid chloride, 2-phenylpropionic acid, 3-phenylpropionic acid, o-
Tolyl acetic acid, m-tolyl acetic acid, p-tolyl acetic acid, cumene acid and the like can be mentioned. These esterifying agents can be used alone or in combination of two or more.

The amount used is 10 mol% based on the number of hydroxyl groups.
The upper limit is not particularly limited, and the excess esterification agent may be removed after the completion of the reaction when excess is used and the esterification is sufficiently advanced. From the viewpoint of the above, the molar amount is preferably 10 times or less, preferably 5 times or less, more preferably 3 times or less with respect to the hydroxyl group.

The specific reaction varies depending on the kind of the esterifying agent, but if each is described, the reaction generally used may be used for the organic carboxylic anhydride. That is, after reacting an arbitrary amount of an organic carboxylic anhydride to be esterified with a phenolic hydroxyl group,
By removing by-produced organic carboxylic acid and excess organic carboxylic anhydride by any method such as atmospheric distillation, vacuum distillation, washing with water, washing with a weak base such as carbonate, or a combination thereof, the desired ester To obtain the compound. That is, in the partially esterified product, it is preferable to use an esterified product in which an arbitrary amount, preferably 10 mol% or more, of the phenolic hydroxyl group is esterified. The upper limit is not particularly limited as long as the solvent is used, and the upper limit thereof is not particularly limited as long as the solvent is used in an amount of at least equimolar to the phenolic hydroxyl group. To esterify. This amount is the same in the case of a reaction using an organic carboxylic acid described later.

The esterification temperature is from 60 ° C. to 200 ° C.
C., preferably from 80.degree. C. to 180.degree. C., particularly preferably from 100.degree. The esterification reaction time largely depends on the type of the reaction substrate and the reaction temperature, but is in a range of about 1 hour to 25 hours.
In practice, it is desirable to determine the end point while tracking the disappearance of the esterifying agent, the disappearance of the hydroxyl group, and the like by high performance liquid chromatography, gas chromatography, or the like.

The solvent in the esterification reaction may or may not be used. None if the phenolic hydroxyl group-containing substance as the raw material is sufficiently molten at the reaction temperature and the esterifying agent is liquid, The reaction may be performed with a solvent.

When a solvent is required, any solvent which is inert to the reaction can be used. Examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, halogenated benzenes such as chlorobenzene and o-dichlorobenzene, N, N-dimethylformamide,
Aprotic polar solvents such as N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N, N-dimethyl-2-imidazolidinone, dimethyl sulfoxide, sulfolane, diphenyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether; Ethers such as diethylene glycol dimethyl ether and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone can be used alone or in any combination. The esterification reaction may be performed at normal pressure, increased pressure (in an autoclave), or reduced pressure, and the atmosphere of the reaction system may be any of air, an inert gas such as nitrogen, argon, or helium. Under the atmosphere.

Next, the reaction when an organic carboxylic acid halide is used as the esterifying agent will be described.
Also in this case, a generally used technique can be used. That is, any amount of an organic carboxylic acid halide to be esterified with the phenolic hydroxyl group may be reacted. In this case, the by-produced hydrogen halide is trapped in the system in the presence of a necessary amount of a base inert to the reaction of pyridine, piperazine, triethylamine, etc. And
There is a method of trapping using water or an alkali trap installed outside the reaction system.However, for the reasons described above, hydrogen halide gas must be supplied quickly during the reaction to avoid contamination with nitrogen-containing compounds and ionic compounds. Preferably, the method is to release the solution outside the system. At this time, it is more preferable to carry out the reaction under a stream of a gas inert to the reaction.

The amount of the organic carboxylic acid halide to be used is as follows. In the case of the partially esterified product, an arbitrary amount, preferably 10 mol% or more, of the phenolic hydroxyl group is esterified. Using a carboxylic acid halide, in a complete esterified product, an equimolar or small excess with respect to the phenolic hydroxyl group may be used, and a large excess may be used, but the economic efficiency, the volumetric efficiency of the reaction, and the In view of the complexity, esterification may be carried out in a range of 10 moles or less, preferably 5 moles, more preferably 3 moles, of the hydroxyl group. The reaction temperature, the use of a solvent in the reaction, and the form of the reaction may be in accordance with the case of the organic carboxylic anhydride.

In the case where an organic carboxylic acid is used as the esterifying agent, an organic carboxylic acid anhydride may be substantially used, but an acid catalyst is required for the reaction. Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and polyphosphoric acid; organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, dimethylsulfonic acid, and diethylsulfonic acid; and trifluoromethane. Examples thereof include a super strong acid represented by sulfonic acid, an acidic ion exchange resin represented by alkane sulfonic acid type, and a super strong acid ion exchange resin represented by perfluoroalkane sulfonic acid type.

The amount of the superacid used is 0.00001 to 5% by mass, preferably 0.1% by mass, based on the weight of the raw material.
0001 to 1% by mass, more preferably 0.001 to 0.1% by mass, in the case of ion exchange resins, 1 to 100% by mass, preferably 10 to 50% by mass;
In other cases, the content is 0.01 to 10% by mass, preferably 0.1 to 5% by mass. Below this range, the reaction rate will decrease and will not be complete in a realistic reaction time. On the other hand, if it is larger than this range, side reactions cannot be ignored, or the cost will increase, including the complexity of the catalyst removal process.

The reactions of the three types of esterifying agents have been described above. In any case, when it is necessary to obtain an esterified product having a higher degree of purification, a washing step may be introduced after the completion of the reaction. Good. In that case toluene,
The esterification reaction may be performed using a water-washable solvent such as xylene, methyl isobutyl ketone, methyl ethyl ketone, or ethyl acetate, and the washing wastewater may be washed until acidic components and ionic impurities are not mixed. The esterification rate of the esterified product is in the range of 10 mol% to 100 mol%, preferably in the range of 50 mol% to 100 mol%, more preferably in the range of 90 mol% to 100 mol%.

The method for determining the content of the polyhydric phenol curing agent (2) in the sealant composition for a liquid crystal display element is as follows.
Although not particularly limited, for example, chromatographic preparative method, infrared absorption spectrum method (IR method), functional group analysis method,
What is necessary is just to perform solution / solid-state NMR (nuclear magnetic resonance spectrum) method suitably combining. The method for determining the content of the polyhydric phenol curing agent (2) in the sealant for a liquid crystal display cell is not particularly limited. NMR
Method, an infrared absorption spectrum method or the like may be appropriately combined.

In the composition for a liquid crystal display cell sealant of the present invention, any known latent epoxy curing agent may be used in combination as the polyhydric phenol curing agent (2) as long as the object of the present invention is not impaired. no problem. As the latent epoxy curing agent, any substance that can substantially cure the epoxy resin by heating at 50 ° C. or more can be preferably used.

The latent epoxy curing agent is not particularly restricted but includes, for example, dicyandiamide and its derivatives, dihydrazide compounds, 4,4-diaminodiphenylmethane, 4,4-diaminodiphenylsulfone, imidazole compound-epoxy resin adducts And its complex, polyamine compound-epoxy resin adduct, polyamine-diisocyanate compound adduct,
Boron trifluoride-amine complex, organic acid anhydride and the like can be mentioned, and one or more of them can be used.

Preferred latent epoxy curing agents include:
One or more selected from dihydrazide compounds, imidazole compound-epoxy resin adducts and complexes thereof, and organic acid anhydrides. (Dihydrazide compound) Preferred specific examples of the dihydrazide compound include, for example, saturated fatty acids having 4 to 22 carbon atoms such as succinic dihydrazide, adipic dihydrazide, sebacic dihydrazide, azelaic dihydrazide, decane diacid dihydrazide, and dodecane diacid dihydrazide. Examples include aromatic dibasic acid dihydrazides represented by dibasic acid dihydrazides having a skeleton, isophthalic acid dihydrazide, and the like, and dihydrazides having a valine hydantoin skeleton. As the dihydrazide compound, a dihydrazide compound derived from a dicarboxylic acid compound having 4 to 22 carbon atoms is more preferable.

(Imidazole Compound-Epoxy Resin Adduct) As a specific example of the adduct of the imidazole compound and the epoxy resin, for example, the mass of the adduct of the polyfunctional epoxy compound, the imidazole compound, and the mass of the polyfunctional epoxy compound is twice or more. Of the reaction product with a small amount of a phenol novolak resin, wherein the ratio of the epoxy group to the molecule of the imidazole compound in the polyepoxy compound is (0.8: 1)
To (2.2: 1). Further, an adduct obtained by mixing a neutralizable amount of a polyhydric phenol monomer and / or a polyhydric phenol resin with the adduct is also included.

(Adduct of Polyamine Compound and Epoxy Resin) The adduct of polyamine compound and epoxy resin is not particularly limited, but may be an adduct derived from a known polyamine compound and epoxy resin. Be represented. Specific examples include adducts obtained by reacting a compound having two or more acidic hydroxyl groups with an addition reaction product of an epoxy resin and a polyamine. Examples of the compound having two or more acidic hydroxyl groups include a phenol resin, a polyphenol resin, and a polycarboxylic acid.

(Adduct of amine compound and diisocyanate compound or modified derivative thereof) As an adduct of amine compound and diisocyanate compound, known adducts of primary and secondary amine compounds and diisocyanate can be used. Represented by an adduct obtained by reacting Examples of the modified derivative of the adduct of an amine compound and a diisocyanate compound include, for example, an adduct obtained by heating and reacting N, N-dialkylaminoalkylamine, a cyclic amine, and diisocyanate. . Further, the adduct body has a softening point of 60 ° C. or more and 3
Examples thereof include a composition obtained by uniformly contacting a diisocyanate compound with the particle surface of a powdery adduct having a secondary amino group.

(Organic acid anhydride) Examples of the organic acid anhydride include phthalic anhydride, maleic anhydride, trimellitic anhydride, ethylene glycol bistrimellitate, pyromellitic anhydride, dodecinyl succinic anhydride, hexahydrophthalic anhydride. Examples thereof include acid, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride and the like. In addition, a part of the latent epoxy curing agent may be selected and used as the following curing accelerator.

(3) Curing Accelerator The curing accelerator (3) used in the composition for a liquid crystal display cell sealant of the present invention is at least one selected from an alkyl urea derivative and a phosphazene compound.

(Alkyl urea derivative) Specific examples of the alkyl urea derivative include, for example, 3- (p-chlorophenyl) -1,1-dimethylurea and 3- (o, p-dichlorophenyl) -1,1-dimethylurea 2,4- [bis (1,1-dimethylurea)] toluene and / or 2,6 derived from tolylene diisocyanate and dimethylamine
-[Bis (1,1-dimethylurea)] alkylurea derivative having an isophorone skeleton derived from toluene, isophorone diisocyanate and dimethylamine, 3,
5-di (1,1-dimethylurea) -5-methyl-2-
Representative examples include cyclohexen-1-one, an alkylurea derivative having a norbornane skeleton derived from norbornane diisocyanate and dimethylamine, and the like. Particularly preferred is 3- (p-chlorophenyl) -1,1
-Dimethylurea, 2,4- [bis (1,1-dimethylurea)] toluene and / or 2,6- [bis (1,1-dimethylurea)] toluene.

(Phosphazene compound) The phosphazene compound is represented by a compound represented by the following chemical formula (12).

[0177]

Embedded image (Wherein, R ^{a to} R ^f represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group or aralkyl group having 6 to 10 carbon atoms, all of which are the same; May also be different.)

R ^{a to} R ^f represented by the above formula (12)
Specific examples of a hydrogen atom, a methyl group, an ethyl group, n
-Propyl group, isopropyl group, n-butyl group, sec
-Butyl group, tert-butyl group, 1-pentyl group, 2
-Pentyl group, 3-pentyl group, 2-methyl-1-butyl group, isopentyl group, tert-pentyl group, 3-methyl-2-butyl group, neopentyl group, n-hexyl group, 4-methyl-2-pentyl Group, cyclopentyl group,
Cyclohexyl group, 1-heptyl group, 3-heptyl group,
Aliphatic hydrocarbon groups such as 1-octyl group, 2-octyl group, 2-ethyl-1-hexyl group, nonyl group or decyl group, phenyl group, toluyl group, benzyl group, 1-phenylethyl group or 2-phenyl Examples include an aromatic hydrocarbon group such as an ethyl group. Among them, preferred are an aliphatic hydrocarbon group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group or a cyclohexyl group, more preferably a methyl group. , An ethyl group.

The phosphazene compound was obtained from GN Koian et.
al.Journal of General Chemistry of The USSR,
As described in 55,1453 (1985), phosphorus oxytrichloride has three molecules of iminotrisamino (unsubstituted, monosubstituted,
(Disubstituted) phosphorane. Further, if purification is necessary, it can be purified by a commonly used method such as column chromatography, distillation and recrystallization. The phosphazene compound thus obtained is usually a solid.

Preferred examples of the phosphazene compound include those represented by the following chemical formula (13).

[0181]

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In the composition for a liquid crystal display cell sealant of the present invention, it is important to contain the curing accelerator (3) in the range of 0.1 to 20% by mass. When the content is 0.1% by mass or more, the curing activity of the curing agent (2) can be sufficiently extracted at the time of heat curing. If used within 20% by mass,
The object of the present invention can be solved without deteriorating the storage stability of the obtained epoxy resin composition at 25 ° C.

Particularly preferred examples of the curing accelerator (3) of the composition for a liquid crystal display cell sealant of the present invention include 3- (p-chlorophenyl) -1,1-dimethylurea and 2,4- [bis
(1,1-dimethylurea)] toluene, 2,6- [bis (1,1
-Dimethylurea)] toluene, or one selected from the phosphazene compounds represented by the chemical formula (12), and most preferably a phosphazene compound represented by the chemical formula (13).

The curing accelerator (3) has a total alkali metal content of 50 pp as determined by flame elemental analysis of a wet decomposition product.
m or less, preferably 30 ppm or less, more preferably 1 ppm or less.
5 ppm or less. By doing so, it is possible to suppress unnecessary transfer of free ions to the liquid crystal phase when the composition for a liquid crystal display cell sealant of the present invention or the liquid crystal display cell sealant which is a cured product thereof comes into contact with the liquid crystal. The purification method for reducing the total content of alkali metals to 50 ppm or less is not particularly limited, and a known method such as a solvent extraction purification method can be applied. The method of determining the type and amount of the curing accelerator (3) in the composition for a liquid crystal display cell sealant of the present invention is not particularly limited. For example, a solvent is extracted and the extract is subjected to GPC. In general, a method of separating and identifying and identifying and quantifying by infrared absorption spectrum or NMR (nuclear magnetic resonance spectrum), an elemental analysis method, and the like are common. Further, as a means for grasping the type and amount of the curing accelerator in the liquid crystal display cell sealant as a cured body,
Although not particularly limited, for example, a thermal decomposition-chromatographic preparative method, a wet decomposition-chromatographic preparative method, a pyrolytic gas chromatography method, a thermal decomposition-mass spectrometry method, a solid state NMR method, or the like may be appropriately combined.

As the curing accelerator (3), other curing accelerators described below may be used in combination as long as the effects of the composition for a liquid crystal display cell sealant of the present invention are not impaired. Other curing accelerators include imidazole compounds and salts thereof, trisdimethylaminomethylphenol salts, 1,8-diazabicyclo (5,4,0) undecene-7 salts, 1,8-diazabicyclo (5,4,0) Undecene-7 salts, 1,5-diazabicyclo (4,3
0) -Nonene-5 salts, 6-dibutylamino-1,8-
One or more selected from diazabicyclo (5,4,0) -undecene-7 salts and the like.

(Imidazole compound) Specific examples of the imidazole compound are not particularly limited.
It can be represented by cyanoethyl-2-ethyl-4-methylimidazole and the like. (Imidazole salts) Examples of the imidazole salts include an isocyanuric acid adduct of an imidazole compound and a polyvalent carboxylic acid adduct of an imidazole compound. (Trisdimethylaminomethylphenol salt) Examples of the trisdimethylaminomethylphenol salt include trisdimethylaminomethylphenol octylate, trisdimethylaminomethylphenol oleic acid, and trisdimethylaminomethylphenol formate.

(1,8-diazabicyclo (5,4,0)
Undecene-7 salt) 1,8-diazabicyclo (5,4,
0) Undecene-7 salt (hereinafter, simply referred to as DBU salt) includes, for example, DBU phenol salt, DBU polyphenol compound salt, DBU polyphenol salt, DBU octylate, DBU oleate, DBU formate, and the like. This is a typical example. (1,5-diazabicyclo (4,3,0) -nonene-5
Salt) 1,5-diazabicyclo (4,3,0) -nonene-
Five salts (hereinafter simply referred to as DBN salts) include, for example, D
BN phenol salt, DBN polyphenol compound salt, D
BN polyphenol salt, DBN octylate, DBN oleate, DBN formate, DBN paratoluenesulfonate and the like are typical examples.

(6-dibutylamino-1,8-diazabicyclo (5,4,0) -undecene-7 salt) 6-dibutylamino-1,8-diazabicyclo (5,4,0) -undecene-7 salt ( Hereinafter, simply referred to as DB salt), for example, DB phenol salt, DB polyphenol compound salt, DB polyphenol salt, DB octylate, DB oleate, DB formate, DB paratoluene sulfonate, etc. This is a typical example.

(4) Rubber-like polymer fine particles having a softening point temperature of 0 ° C. or less and primary particles having an average particle diameter of 5 μm or less In the composition for a liquid crystal display cell sealant of the present invention, if necessary, a torsional pendulum may be used. Torsinal called law
Rubber-like polymer fine particles having a softening point temperature of 0 ° C. or less at a softening point temperature determined by a Braid Analyzer (hereinafter, simply referred to as TBA) and an average primary particle diameter of 5 μm or less determined by electron microscopic observation ( 4) (Hereinafter,
Sometimes referred to simply as rubber-like polymer fine particles. ) Is preferably contained in an amount of 1 to 25% by mass. At that time, the rubber-like polymer fine particles had an average particle size of the primary particles of 0.0
The thickness is preferably 1 to 5 μm, more preferably 0.05 to 2 μm.

By using 1% by mass or more of the rubber-like polymer fine particles in the composition for a liquid crystal display cell sealant of the present invention, the composition of the liquid crystal display element itself produced using the composition for a liquid crystal display cell sealant of the present invention can be obtained. The adhesion reliability after the pressure cooker test can be improved by 25% by mass.
By setting the following, it is possible to secure the heat resistance required for the cured body,
preferable. In particular, the proportion of the rubber-like polymer fine particles (4) in the composition for a liquid crystal display cell sealant is 1 to 20.
The content is more preferably in the range of 1% by mass, particularly preferably 1% to 15% by mass.

Further, it is preferable that the softening point temperature of the rubber-like polymer fine particles (4) is 0 ° C. or less, since the adhesion reliability at a low temperature tends to be further improved. Further, by setting the primary particle diameter of the rubber-like polymer fine particles (4) to 5 μm or less, the gap of the liquid crystal cell can be reduced, the amount of expensive liquid crystal used can be suppressed, and the liquid crystal display response speed can be reduced. Can also be improved. Still more preferred rubber-like polymer fine particles (4) include -30
℃ or less, its primary particle size is 0.01
Silicon rubber fine particles and / or acrylic rubber fine particles or polyolefin rubber fine particles having a size of from 2 to 2 μm, more preferably the rubber-like polymer fine particles (4) are crosslinkable rubber particles.

As long as the softening point temperature of these rubber-like polymer fine particles (4) is 0 ° C. or lower, the following known rubber-like polymers can be appropriately selected and used. For example, acrylic rubber-based rubber polymer, silicone rubber-based rubber polymer, conjugated diene rubber-based rubber polymer, olefin rubber-based rubber polymer, polyester rubber-based rubber-based polymer, urethane rubber-based rubber-based polymer, composite rubber And a rubber-like polymer having a functional group that reacts with an epoxy group. In particular, among these rubbery polymers, those having a functional group that reacts with an epoxy group are preferable. The rubber-like polymer fine particles (4) used in the composition for a liquid crystal display cell sealant can be used alone or as a mixture of two or more of them. Specific examples of these rubber-like polymer fine particles are shown below.

<Acrylic rubber-based rubber-like polymer fine particles> Specific examples of the acrylic rubber-based rubber-like polymer fine particles include, for example, a core / core having an acrylic rubber core.
Particles obtained by drying the shell emulsion,
A resin composition obtained by non-aqueous dispersion polymerization of an acrylic monomer in an epoxy resin, and further, an acrylic rubber polymer solution obtained by introducing a functional group that reacts with an epoxy group is separately adjusted and then put into the epoxy resin or There is a resin composition in which acrylic rubber fine particles are stably dispersed in an epoxy resin by dropping, mechanically mixing, desolvating or grafting, and the like.

<Silicon rubber-based rubber-like polymer fine particles> Specific examples of silicon rubber-based rubber-like polymer fine particles include powdery silicon rubber fine particles,
A resin composition in which a double bond is introduced into an epoxy resin and reacted with a silicon macromonomer having an acrylate group at one end capable of reacting with the double bond, and then vinyl silicon and hydrogen silicon are charged and dispersion polymerized. There is.

<Conjugated diene rubber-based rubber-like polymer fine particles> Specific examples of conjugated diene rubber-based rubber-like polymer fine particles include, for example, 1,3-butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, Examples thereof include conjugated diene rubber-like polymer fine particles obtained by polymerizing or copolymerizing a monomer such as chloroprene, which may be a known material, and is not particularly limited. Commercial products can be used as they are. Examples of more specific conjugated diene rubber include a copolymer of butadiene and acrylonitrile,
Copolymers of butadiene having a carboxyl group at the terminal and acrylonitrile, and copolymers of butadiene having an amino group at the terminal and acrylonitrile are exemplified.

<Olefin rubber-based rubber-like polymer fine particles> Specific examples of olefin rubber-based rubber-like polymer fine particles include, for example, ethylene, propylene, 1-butene,
Examples thereof include fine particles composed of a homo-amorphous polymer such as 2-butene and isobutene or a copolymer or terpolymer with another copolymerizable monomer, or a composition thereof. A resin composition obtained by dehydrating a commercially available product such as an olefin rubber latex in an epoxy resin to stabilize the dispersion of the olefin rubber in the epoxy resin is also a good example.

<Polyester Rubber-Based Rubber-Like Polymer Fine Particles> The polyester rubber-based rubber-like polymer fine particles are fine particles made of a rubber-like polymer having a polymer skeleton containing a polyester bond, and are not particularly limited. Specific examples of the polyester rubber include, for example, at least one diol component selected from liquid polysiloxane diol, liquid polyolefin diol, polypropylene glycol, polybutylene glycol, and the like, and a polyhydric alcohol such as triol or more, if necessary. A low-softening point polyester resin derived from at least one dibasic acid selected from adipic acid, maleic acid, succinic acid, phthalic acid, and the like in the presence of a compound; Examples thereof include a low softening point polyester resin using an anhydride and a low softening point polyester resin derived from a hydroxy polycarboxylic acid or the like.

<Urethane rubber-based rubber-like polymer fine particles>
The urethane rubber-based rubber-like polymer fine particles are fine particles made of a rubber-like polymer having a rubber-like polymer skeleton containing a urethane bond and / or a urea bond, and are not particularly limited. Specific examples of the urethane rubber include, for example, a diol component composed of at least one selected from liquid polysiloxane diol, liquid polyolefin diol, polypropylene glycol, polybutylene glycol, and the like, and, if necessary, polyhydric triol or more. In the presence of an alcohol compound, by reacting with a known diisocyanate compound represented by hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, norbornane diisocyanate, etc. The rubbery polyurethane obtained, further, for example, at least one long-chain diamine component selected from liquid polysiloxane diamine, liquid polyolefin diamine, polypropylene glycol diamine, etc. Under the coexistence of a polyamine compound of at least min, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, already known diisocyanate compounds represented by norbornane diisocyanate, etc. And a rubber-like polyurethane obtained by the action of

<Composite Rubber Particles> Examples of the composite rubber particles include, for example, a graft polymer and / or a block polymer comprising two or more of the above-mentioned acrylic, silicon, conjugated diene, olefin, polyester, and urethane types. Alternatively, fine particles composed of a core-shell polymer, a multilayer polymer, or the like can be exemplified.

<Rubber-like Polymer Having Functional Group Reacting with Epoxy Group> Examples of the rubber-like polymer having a functional group reacting with an epoxy group include the above-mentioned acrylic, silicone, conjugated diene, olefin, and polyester. A typical example is a product obtained by introducing a functional group that reacts with an epoxy group into urethane-based particles. In the rubber-like polymer having a functional group that reacts with the epoxy group, the repeating structure derived from the monomer having a functional group that reacts with the epoxy group accounts for 0.1 to 25% by mass in the rubber-like polymer. Preferably, there is. The adhesiveness of the composition for a liquid crystal display cell sealant obtained by adjusting the content of the repeating structure derived from a monomer having a functional group which reacts with an epoxy group to 0.1% by mass or more and 25% by mass or less is remarkable. improves.

The functional group capable of reacting with the epoxy group includes
Examples include a mercapto group, an amino group, an imino group, a carboxyl group, an acid anhydride group, an epoxy group, a hydroxyl group and the like. The rubbery polymer preferably has at least one of these functional groups introduced therein in an amount of 0.01 to 25% by mass, more preferably 0.1 to 10% by mass.

The method for introducing a functional group is not particularly limited.
Random copolymerization method, alternating copolymerization method, condensation polymerization method, addition polymerization method, introduction method by core-shell polymerization method, ion adsorption introduction method, swelling impregnation introduction method of functional group-containing monomer and monomer constituting main chain polymer And any method such as a method of graft polymerization to a polymer that forms rubber-like particles. Among them, copolymerization, graft polymerization method,
It is preferable because a necessary functional group can be efficiently introduced near the surface of the rubber-like polymer fine particles with a small amount.

In the composition for a liquid crystal display cell sealant of the present invention, it is preferable that the rubber-like polymer fine particles (4) maintain their shape as particles in an epoxy resin. The means for determining that the rubber-like polymer fine particles (4) are present as particles in the epoxy resin is not particularly limited. For example, a mixture of a non-turbid epoxy resin and rubber-like polymer fine particles may be prepared. A method for observing the composition with an optical microscope to confirm that the rubber-like polymer fine particles are present as particles, and a cured product obtained by adding a predetermined amount of a polymercaptan-based curing agent to the composition and curing the composition. The method of sensitizing the fractured surface of the micro-section with osmic acid staining, observing it with a scanning electron microscope, and confirming the presence of particles can be appropriately adopted.

In the composition for a liquid crystal display cell sealant of the present invention, the rubber-like polymer fine particles (4) may or may not be grafted in advance with the epoxy resin (1). The method for grasping the kind, amount and particle size of the rubber-like polymer fine particles (4) in the composition for a liquid crystal display cell sealant and the sealant for a liquid crystal display cell of the present invention is not particularly limited. For example, a scanning electron microscope image (SE
M) or a method of confirming the particle image with a transmission electron microscope (TEM) after sensitizing the fragment with osmic acid staining, or comparing the elemental analysis image with SEM observation. Identification and quantification method, method of determining and determining the micro layer by measuring the infrared absorption spectrum of the micro layer, method of identifying and determining the gas component which is decomposed and generated by irradiating the micro layer with heat rays, volume specific volume of the micro layer The method can be carried out by appropriately combining a method of obtaining a mass ratio by converting from the above.

(5) Inorganic Filler The inorganic filler (5) may be any one as long as it can be generally used as an inorganic filler in the field of electronic materials.
Specifically, for example, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, aluminum oxide (alumina), zinc oxide, silicon dioxide, potassium titanate, kaolin, asbestos powder And amorphous silica powder, quartz powder, mica, glass fiber, carbon black, silicon nitride, aluminum nitride, titanium trinitride and the like, and one or more of these can be used in combination. Preferred inorganic fillers (5) are high-purity silica and / or high-purity alumina or titanium oxide.

More preferably, the total content of the alkali metals determined by atomic absorption spectrometry of the wet decomposition product is 50 pp.
m, more preferably 30 ppm or less, particularly preferably 15 ppm or less, high-purity silica and / or high-purity alumina or titanium oxide. By using these, transfer of free ions from the cured product of the sealant composition for a liquid crystal display element of the present invention to the liquid crystal phase can be suppressed. There is no particular limitation on the purification method for reducing the total content of alkali metals to 50 ppm or less. For example, an aqueous solution can be obtained at the stage of a production raw material, and it can be obtained by a purification method such as an ion exchange purification method.

The inorganic filler (5) was 632.8.
It is preferable that the ⁹⁹ % by weight particle diameter value (d ⁹⁹ ) on the weighted product curve determined by a laser particle size analyzer having a wavelength of nm is 5 μm or less, and it is indicated by the 50% by weight value on the mass added curve. Weight average particle diameter value (d ⁵⁰ ) is 0.005
More preferably, it is in the range of 1 to 1 μm. Generally, it is preferable to use an inorganic filler having a d ⁹⁹ of 5 μm or less, because the dimensional stability of the gap width of the liquid crystal panel is further improved.

In the sealant composition for a liquid crystal display device of the present invention, the inorganic filler (5) is used as needed.
A preferable content ratio is 5 to 45% by mass. 5
By containing at least 50% by mass, screen printing or dispenser application workability can be improved, and at 45% by mass or less, the fluidity of the composition can be ensured, without causing blurring or clogging of the dispenser during screen printing. Coating work is preferable. In particular, the range of 10 to 40% by mass is preferable.

The inorganic filler (5) is not particularly limited, but it is preferable to use it after being graft-modified with an epoxy resin (1) or a silane coupling agent (6) in advance. In the graft modification, a part or all of the inorganic filler (5) may be graft-modified. At this time, the grafting ratio is represented by a mass increase rate obtained by a repeated solvent washing method, and is usually one of the epoxy resin (1) and the silane coupling agent (6) per 100 parts by mass of the inorganic filler (5). Or 1 to 5 of both
Preferably, 0 parts by weight are chemically bonded.

The method for determining the type and amount of the inorganic filler (5) in the composition for a liquid crystal display cell sealant of the present invention is not particularly limited, but examples thereof include a filtration preparative method and an X-ray diffraction method. What is necessary is just to perform a spectrum method, an elemental analysis method, a heating incineration residue method, a wet pyrolysis-atomic absorption method, an electron microscope observation image analysis method, etc. suitably combining. Means for grasping the type and amount of the inorganic filler in the liquid crystal display cell sealant as a cured product thereof is not particularly limited, but includes, for example, an X-ray diffraction spectrum method, an elemental analysis method, and the like. The heat incineration residue method, wet pyrolysis-atomic absorption method, electron microscopic observation image analysis method and the like may be appropriately combined, and there is no particular limitation.

(6) Silane Coupling Agent In the sealant composition for a liquid crystal display element of the present invention, a silane coupling agent (6) is used if necessary, but the preferable content is 0.1 to 5% by mass. It is. Adhesion to the glass substrate can be secured by using 0.1% by mass or more,
Further, even if it is used in an amount exceeding 5% by mass, no remarkable effect can be obtained. Preferably 0.5 to 3% by mass
It is.

As the silane coupling agent (6), any of the commonly used ones can be used, and examples thereof include trialkoxysilane compounds and methyldialkoxysilane compounds. Preferably, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropylmethyldiethoxysilane, γ-
Glycidoxypropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-aminoethyl-γ-amino Propylmethyldimethoxysilane, N-aminoethyl-γ-aminopropyltrimethoxysilane, N-aminoethyl-γ-aminopropylmethyldiethoxysilane, N-phenyl-γ
-Aminopropyltrimethoxysilane, N-phenyl-
γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropylmethyldiethoxysilane,
γ-mercaptopropylmethyldimethoxysilane, γ-
Examples thereof include mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatopropyltriethoxysilane. Among them, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-phenyl-γ-
One or more selected from aminopropyltrimethoxysilane and γ-isocyanatopropyltriethoxysilane are more preferred.

The method for determining the type and amount of the silane coupling agent (6) in the composition for a liquid crystal display cell sealant of the present invention is not particularly limited, but examples thereof include a solvent extraction fractionation method and an NMR spectrum. The identification method, gas chromatography method, distillation fractionation method and the like may be appropriately combined.
Means for grasping the type and amount of the silane coupling agent in the liquid crystal display cell sealant, which is a cured product thereof, are not particularly limited. And the like can be appropriately combined, and there is no particular limitation.

(7) Solvent In the composition for a liquid crystal display cell sealant of the present invention, an epoxy group having a boiling point in the range of 150 to 220 ° C., which is further compatible with an epoxy resin, relative to 100 parts by mass of the composition. The inert solvent (7) may be contained in the range of 1 to 25 parts by mass. By including the solvent, the suitability for screen printing and the wettability to the adherend can be improved. Preferably, a high boiling solvent having a boiling point in the range of 160 to 200 ° C. is used.

Specific examples of the solvent (7) are not particularly limited, but preferred examples thereof include a ketone solvent such as cyclohexanone, an ether solvent and an acetate solvent. Specific examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dipropyl. Ether, ethylene glycol dibutyl ether, ethylene glycol diphenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, diethylene glycol dimethyl ether, diethylene glycol Lumpur diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol diphenyl ether.

Further, the acetate solvent is preferably
For example, ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diacetate, diethylene glycol monomethyl acetate, diethylene glycol monoacetate Ethyl acetate,
Diethylene glycol monobutyl ether acetate,
And diethylene glycol diacetate.

Particularly preferred solvent (7) is selected from ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol diacetate. At least one of them.

There is no particular limitation on the method of finding the type of solvent and the ratio thereof in the composition for a liquid crystal display cell sealant.
For example, a drying loss method, a gas chromatography (preparation) method, a distillation separation method, a gas mass method, an infrared absorption spectrum method, an NMR method, or the like may be appropriately combined.

(8) High softening point polymer fine particles having a softening point temperature of 50 ° C. or more and a primary average particle size of 2 μm or less in the composition for a liquid crystal display cell sealant of the present invention. The polymer particles (8) having a high softening point may be contained in the range of 0.1 to 25 parts by mass with respect to 100 parts by mass of the composition. By using 0.1 parts by mass or more, it is possible to further ensure the seal bonding without generation of through bubbles or bleeding in the vacuum single-sheet heat press or rigid single-sheet heat press primary bonding step, Further, it is preferable to use 25% by mass or less in combination, since the gap operability can be sufficiently ensured.

The high softening point polymer fine particles (8) are TB fine particles.
Acrylic polymer fine particles having a high softening point having a softening point temperature of 50 ° C. or more at the softening point temperature obtained from A and having an average primary particle diameter of 2 μm or less observed by an electron microscope (8)
(Hereinafter sometimes simply referred to as high softening point polymer fine particles). Acrylic polymer fine particles with high softening point (8)
By setting the average particle diameter of the primary particles to 2 μm or less, the gap operability can be ensured. The average particle size of the primary particles is preferably in the range of 0.01 to 1 μm,
More preferably, it is in the range of 0.2 to 0.5 μm.

The high softening point acrylic polymer fine particles (8) can be used in either a crosslinked type or a non-crosslinked type.
A crosslinked type is preferable, and particularly high softening point acrylic polymer fine particles having a finely crosslinked structure are more preferable. The high softening point acrylic polymer fine particles having a finely crosslinked structure are produced by making the crosslinkable monomer in the range of 0.1 to 5% by mass, preferably 1 to 3% by mass in all the monomers when producing the polymer. be able to.

One of the indexes of the degree of fine crosslinking is a gel fraction. This means that 10 g of high softening point polymer
After dispersing in 0 g of methyl carbitol solvent, stirring at 25 ° C. for 1 hour, filtration, the amount of the filtrate and the polymer content (dissolved amount) in the filtrate were determined. Gel fraction (%) = (dissolved amount / 10 g) × The index is set to 100. The gel fraction index is preferably in the range of 0 to 50%, more preferably 0 to 5%. The high softening point acrylic polymer fine particles preferably have a wetting index calculated from the chemical structural formula of 9 to 11, more preferably 9.3 to 10.5.

Specific examples of the high softening point acrylic polymer fine particles (8) include, for example, finely crosslinked polymethacrylic acid methyl ester main component type obtained by copolymerizing 0.1 to 5% by mass of a crosslinkable monomer. Examples of the polymer include a polymethacrylate methyl ester polymer having an ionomer structure in the range of 0.1 to 5% by mass. In the high softening point acrylic polymer fine particles, it is more preferable that one type of functional group such as an epoxy group, an amino group, an imino group, a mercapto group, and a carboxyl group is introduced on the particle surface. More preferably, it has a softening point temperature of 60 to 150 ° C. and a primary particle size in the range of 0.01 to 1 μm.

In the composition for a liquid crystal display cell sealant of the present invention, the rubber-like polymer fine particles (4) and the high softening point acrylic polymer fine particles (8) may be previously compounded. The so-called core-shell type composite fine particles (A) of (4) and (8) wherein the rubber-like polymer fine particles (4) form a core phase and the high softening point acrylic polymer fine particles (8) form a shell phase. . Also, a preferred embodiment is a mode using the core-shell type composite fine particles (B) having the high softening point acrylic polymer fine particles (8) as the core phase and the rubbery polymer fine particles (4) as the shell phase. In particular, the former embodiment using the core-shell type composite fine particles (A) is preferable. In the core-shell type composite fine particles (A) containing the rubber-like polymer fine particles (4) as the core phase, the core: shell mass ratio is desirably in the range of (1: 0.3) to (1: 2). The method for determining the type or the ratio of the high softening point polymer fine particles in the composition for a liquid crystal display cell sealant or the sealant for a liquid crystal display cell is not particularly limited, and is the same as the method for measuring the rubber-like polymer fine particles. Can be done in a way.

(9) Gap Control Agent In the composition for a liquid crystal display cell sealant of the present invention, a gap control agent (9) is further added to the epoxy resin composition.
Is a more preferred embodiment. The gap control agent (9) is a substance for arbitrarily and accurately adjusting the gap width of the liquid crystal display element to a width of about 3 to 7 μm. Either can be used. It is preferable that the gap-controlling agent (9) is appropriately contained as needed at a ratio of 0.1 to 5 parts by mass with respect to 100 parts by mass of the composition for a liquid crystal display cell sealing agent of the present invention. More preferably, it is in the range of 0.5 to 2.5 parts by mass.

Examples of the gap-controlling agent (9) include, but are not limited to, spherical, rugby ball-like particles, rod-like fibers and the like which are not deformed, dissolved or swollen by the epoxy resin (1) or the solvent (7) used as required. Left and right symmetric inorganic particles or thermosetting polymer particles may be used. Examples of the inorganic particles of the gap formation control agent (9) include spherical silica particles, spherical alumina particles, glass short fibers, metal short fibers, and metal powder. Also,
As the organic gap control agent (9),
Examples include thermosetting polystyrene spherical particles, phenol resin-based thermosetting particles, and benzoguanamine resin-based thermosetting particles. Inorganic particles are a particularly preferable example because the gap accuracy can be controlled with high accuracy.

The method for determining the type of the gap control agent in the composition for a liquid crystal display cell sealant or the sealant for a liquid crystal display cell or the quantitative ratio thereof is not particularly limited. For example, an SEM observation image analysis method of a cured product TEM observation image analysis method, separation filtration method, pyrolysis gas chromatography method, heating residue X-ray diffraction method, elemental analysis method and the like.

(10) Conductive Beads The composition for a liquid crystal display cell sealant of the present invention is used for the purpose of simultaneously imparting an anisotropic conductivity function together with a sealing function.
As a preferred embodiment, a composition further containing 1 to 15 parts by mass of the conductive beads (10) in combination with 100 parts by mass of the epoxy resin composition is included. By containing the conductive beads at a ratio of 1 to 15 parts by mass, an anisotropic conductive function can be provided. The use of 1 part by mass or more is preferable because a vertical conductivity function can be provided, and the use of less than 15 parts by mass can ensure insulation properties between both lateral (left and right) electrodes. The conductive beads (10) are not particularly limited, but may have an average particle diameter of 3 to 10 for example.
Conductive beads having a diameter of 10 μm, a maximum particle diameter of 10 μm or less, and a minimum particle diameter of 0.1 μm or more are preferred.

The type of the conductive beads is not particularly limited, but specific examples are shown below. For example, noble metal particles, noble metal alloy particles, base metal particles, base metal alloy particles, other metal-coated organic particles, and metal-coated insulating inorganic particles may be used.

(Noble metal) For example, gold, silver, platinum and the like can be exemplified. (Noble metal alloy) For example, silver / copper alloy, gold / copper alloy, gold / copper alloy
Silver alloy, platinum / silver alloy, gold / platinum alloy, gold / nickel alloy, silver / nickel alloy and the like can be exemplified.

(Base Metal) For example, copper, nickel, tin, tungsten and the like can be exemplified. (Base metal alloy) For example, copper / nickel alloy, copper / tin alloy, solder and the like can be exemplified.

(Metal-Coated Organic Matter Particles) A typical example is formed by forming the conductive metal film on organic polymer particles represented by polystyrene or polymethyl methacrylate. Sekisui Fine Chemical Co., Ltd. has a trade name "Micropearl AU Series" as a commercially available product, and can be preferably used.

(Metal-Coated Insulating Inorganic Particles) A typical example is formed by forming the conductive metal film on highly insulating inorganic particles represented by mica or glass beads. As the conductive beads, the primary dispersion stability is easily ensured, and the metal-coated organic particles are contained in the composition for a liquid crystal display cell sealing agent of the present invention in an amount of 3 to 7% by volume in the composition.
A preferred embodiment is one in which it is contained. In particular, in the composition for a liquid crystal display cell sealant of the present invention, the conductive beads (10) have an organic polymer as a core and are selected from gold, silver, a gold-copper alloy, a silver-copper alloy, nickel or an alloy thereof. It is preferable to use conductive beads made of at least one kind of metal-coated phase.

The average particle size of the conductive beads is preferably within the above range. When the conductive beads having an average particle size of 1 μm or less are used, it is difficult to obtain good vertical conduction characteristics even if there are conductive particles between the electrodes. On the other hand, if the average particle diameter or the maximum particle diameter exceeds 10 μm, short circuit is likely to occur. The method for determining the type of the conductive beads (conductive particles) in the composition for a liquid crystal display cell sealant or the sealant for a liquid crystal display cell or the quantitative ratio thereof is not particularly limited. TEM or SEM
An image analysis method, a filtration fractionation method and the like can be appropriately combined.

Other Additives In the composition for a liquid crystal display cell sealant of the present invention, if necessary, a wax, a leveling agent, a pigment, a dye, a plasticizer, and an antifoaming agent can be used.

(11) Wax In the composition for a liquid crystal display cell sealant of the present invention, the wax (11) is used mainly for the purpose of improving the low moisture permeability function and further improving the low water absorption while maintaining the adhesiveness. Can be used. The use ratio of the wax (11) is 100% of the composition for a liquid crystal display cell sealant of the present invention.
The wax is preferably contained in an amount of 0.1 to 5% by mass with respect to the mass part. By setting the wax to 0.1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the composition for a liquid crystal display cell sealant, the cured product is subjected to a high-temperature and high-humidity environment of 80 ° C. and a relative humidity of 95% or more. The moisture permeability of the cured product at 80 ° C. can be further reduced. Accordingly, it becomes possible to manufacture a liquid crystal display cell having high durability.

There is no particular limitation on the wax (11), and any wax can be used. For example, animal-based natural wax, plant-based natural wax, mineral-based natural wax, petroleum-based wax, synthetic hydrocarbon-based wax, modified wax, hydrogenated wax and the like can be mentioned. Among them, waxes having a melting point of 70 ° C. or more and 150 ° C. or less are preferable, and carnauba wax, microcrystalline wax, Fischer-Tropsch wax, and modified Fischer-Tropsch wax are more preferable.

In the composition for a liquid crystal display cell sealant of the present invention containing the wax (11), the wax is formed as independent primary particles before the liquid crystal display cell sealant composition is cured. It is preferably present, and the average particle size of the primary particles as observed with an electron microscope or an optical microscope is preferably in the range of 0.01 to 5 μm, and more preferably in the range of 0.01 to 3 μm. Hereinafter, more specific examples of the wax (11) will be described.

(Animal Natural Wax) For example, beeswax,
Whale wax, shellac wax and the like can be mentioned. (Vegetable natural wax) For example, carnauba wax, olicury wax, candelilla wax, wood wax,
Cane wax and the like. (Mineral natural wax) Examples include montan wax, ozokerite, and ceresin. (Petroleum-based wax) Examples include paraffin wax and microcrystalline wax.

(Synthetic hydrocarbon waxes) Examples include Fischer-Tropsch wax and its derivatives, polyethylene wax and its derivatives, and polypropylene wax and its derivatives. (Modified wax) For example, oxidized wax, montan wax, acid-modified wax and the like can be mentioned. (Hydrogenated wax) Examples include amide wax such as stearic acid amide wax, polyester wax, opal wax and the like.

Preparation of Liquid Crystal Display Cell Sealant Composition The liquid crystal display cell sealant composition of the present invention was prepared by the following methods.
(1) epoxy resin, (2) polyhydric phenol curing agent,
(3) a curing accelerator comprising at least one selected from an alkyl urea derivative and a phosphazene compound, and if necessary, further (4) a softening point temperature of 0 ° C. or less, and an average primary particle diameter of 5 μm or less. Rubber-like polymer fine particles, (5) inorganic filler, (6) silane coupling agent, (7) solvent, (8) high softening point polymer fine particles,
(9) Gap control agent, (10) conductive beads, (11) wax, leveling agent, pigment, dye,
Other additives such as a plasticizer and an antifoaming agent may be appropriately added and mixed, and there is no particular limitation. For mixing, for example, a double-armed stirrer, a roll kneader, a twin-screw extruder, or the like, may be performed by using a known machine. Be transported.

Physical Properties of Composition for Liquid Crystal Display Cell Sealant The viscosity of the composition for liquid crystal display cell sealant before curing is not particularly limited, but may be measured with a Brookfield viscometer (B type viscometer) or an E type viscometer. The viscosity at 25 ° C. is preferably in the range of 1 to 1000 Pa · s, and 5 to 500 Pa
S is more preferable, and the range of 10 to 200 Pa · s is most preferable. The composition for a liquid crystal display cell sealant of the present invention is produced by adjusting the viscosity in the above range in advance by a method such as heat curing. In addition, the ratio of the 1 rpm viscosity value obtained from the shear speed of one rotation per minute and the 10 rpm viscosity value at the shear speed of 10 rotations (1 rpm viscosity value / 10 rp
The thixotropic index represented by (m viscosity value) is not particularly limited, but is preferably in the range of 1 to 3.

Method of Manufacturing Liquid Crystal Display Element The method of manufacturing a liquid crystal display element of the present invention is a method of manufacturing TN liquid crystal, STN
In the production of a liquid crystal display element using a liquid crystal, a ferroelectric liquid crystal, and an antiferroelectric liquid crystal, the composition for a liquid crystal display cell sealant of the present invention is printed or bonded on a bonding seal component of a glass or plastic liquid crystal cell substrate. After dispensing, pre-curing at a temperature of 50 to 120 ° C., performing positioning with another substrate and superimposing and temporarily fixing the substrate, the substrate is hot-pressed at 80 to 200 ° C. After bonding and fixing the substrate to a uniform thickness in the range of 3 to 7 μm, a liquid crystal material is injected into the cell, and the injection hole is sealed with a photocurable liquid crystal sealant composition or a two-liquid crystal sealant composition. It is a manufacturing method characterized in that it is obtained by the following method.

Further, another method of manufacturing a liquid crystal display element of the present invention relates to a method of manufacturing a liquid crystal display element using TN liquid crystal, STN liquid crystal, ferroelectric liquid crystal, and antiferroelectric liquid crystal. The composition for printing is printed or dispensed on the bonding seal component of a glass or plastic liquid crystal cell substrate, and after precuring at a temperature of 50 to 120 ° C., the liquid crystal is dropped to prevent the air from being trapped. After superimposing the substrate, aligning and temporarily fixing the substrate, the substrate is subjected to heat-pressing at 80 to 150 ° C.
After bonding and fixing the counter substrate to a uniform thickness in the range of 3 to 7 μm, the breathing hole is obtained by sealing with a photocurable liquid crystal sealant composition or a two-part liquid crystal sealant composition. Manufacturing method.

At this time, in order to completely cure and bond and seal the composition for a liquid crystal display cell sealing agent containing a solvent, precuring is required in advance. Precuring conditions are not particularly limited, but it is general to select a heating and drying temperature at least 95% by mass or more of which can be desolvated and the curing agent contained is not more than the thermal activation temperature when the contained solvent content is 100. And 70 to 120 ° C. is preferable. As general precuring conditions, more preferably, the precuring temperature is in the range of 80 ° C. to 100 ° C., and the heat treatment time is 30 to 5 minutes. The higher the temperature, the shorter the drying time. Solvent removal can be performed even with a precuring temperature exceeding 120 ° C., but care must be taken since the precision of the gap width tends to decrease as the curing reaction proceeds. As a liquid crystal cell substrate to be used, for example,
Glass substrates and plastic substrates can be used. In these substrate groups, it is a matter of course that a transparent electrode represented by indium oxide, an alignment film represented by polyimide, etc., and other inorganic ion shielding films, etc. are applied to necessary parts, so-called glass substrates for liquid crystal cell construction. Alternatively, the same plastic substrate is used.

The method for applying the composition for a liquid crystal display cell sealant to a substrate is not particularly limited, and may be, for example, a screen printing application method or a dispenser application method. After application, after pre-drying as necessary, bonding and bonding by a method of bonding under heat and pressure, there are no particular restrictions on the heat-curing conditions, but at 100 to 200 ° C. It is desirable that the heating time is 24 to 0.5 hour, preferably 24 to 1 hour at 110 to 180 ° C.

When the hot pressing / adhering step is carried out by a single-wafer hot press, the conditions for ensuring the temporary adhesiveness are not particularly limited, but are preferably 110 to 180.
After bonding at 10 ° C. for about 10 to 2 minutes, the pressure is released, taken out, and then subjected to two or more heating steps or curing steps such as complete curing and curing in a heating oven adjusted to the same temperature. Here, the sheet-fed heat press means a heat press machine of a specification for joining one set at a time, and a sheet-fed heat press machine capable of applying heat under vacuum is a vacuum sheet-fed heat press, and under atmospheric pressure. There is known a rigid single-wafer heat breath of a type of forcibly heating and pressing and bonding through a hot plate.
Any single-wafer heat press method may be used. In addition, there is no problem even if a multi-stage hot press is used in the hot press / adhesion process separately from the above-mentioned single-wafer hot press.

Liquid crystal display device The liquid crystal display device of the present invention is obtained by printing or dispensing the composition for a liquid crystal display cell sealant of the present invention on a joint sealing component of a liquid crystal cell substrate made of glass or plastic. After pre-curing at 120 ° C, after positioning with the other uncoated target same substrate,
The counter substrate is heat-pressed at 100 to 200 ° C., and the substrate is bonded and fixed to a uniform thickness in the range of 3 to 7 μm. A liquid crystal material is injected into the cell,
A liquid crystal display element obtained by sealing the injection hole with a two-liquid type liquid crystal sealant composition, or a liquid crystal display cell sealant composition of the present invention is bonded to a glass or plastic liquid crystal cell substrate at a joint sealing component. After printing or dispensing and pre-curing at a temperature of 50 to 120 ° C., the other substrate is overlaid, the liquid crystal is dropped and the air is not trapped, and the substrate is properly fixed. And heat-pressing at 3 ° C.
Manufacturing the liquid crystal display element, which is obtained by bonding and fixing to a uniform thickness in the range of μm, and then sealing the breathing hole with a photocurable liquid crystal sealant composition or a two-part liquid crystal sealant composition. A liquid crystal display device obtained by the method.

The photocurable liquid crystal sealant composition is not particularly limited, but includes, for example, a composition containing a polyvalent acrylate resin and a photoinitiator, and a composition containing an epoxy resin and an ultraviolet photoinitiator. And a resin composition containing an oxetane compound and an ultraviolet light initiator, and a resin composition containing an epoxy resin, oxetane and a photoinitiator.

The two-component liquid crystal sealant composition is not particularly limited. For example, a two-component liquid crystal sealant composition comprising an epoxy resin and a polyamide curing agent, and a two-component liquid crystal composition comprising an epoxy resin and a polythiol curing agent Liquid crystal sealing composition, consisting of epoxy resin and polyamine curing agent 2
Examples thereof include a liquid-type liquid crystal sealant composition. There is no limitation on the liquid crystal material, and for example, a nematic liquid crystal or a ferroelectric liquid crystal can be suitably used.

The liquid crystal display device obtained by the present invention includes:
For example, a TN type (Twisted Nematic) liquid crystal element or an STN type (Super Twisted N) proposed by M. Schadt and W. Helfrich et al.
liquid crystal element or Clark (N.M.
A. Clark) and Ragawell (ST Lagerw)
All), a ferroelectric type liquid crystal element proposed, and a liquid crystal display element in which a thin film transistor (TFT) is provided for each pixel are preferable examples.

[0252]

Hereinafter, the present invention will be described in detail with reference to typical examples and comparative examples, but the present invention is not limited to these examples. The percentages and parts in the examples represent% by mass and parts by mass, respectively. The raw material types (abbreviations) used in each example are as follows. Test Method The methods of the evaluation test performed on the composition for a liquid crystal display cell sealing agent and its cured product in Examples and Comparative Examples are described.

(Storage Stability Test) 100 parts of the composition for a liquid crystal display cell sealant was placed in a polyethylene container, sealed, and the viscosity at 20 ° C. when sealed was set to 100.
° C / expressed by the rate of change of the viscosity value after 30 days. 〇: Good storage stability with a change rate of less than 10% △: Somewhat problematic in storage stability with a change rate of 10 to 50% ×: Change in excess of 50%, poor storage stability

(Coating workability test) The composition for a liquid crystal display cell sealing agent hermetically sealed and stored in a polyethylene container below the freezing point was taken out and returned to room temperature of 25 ° C. over 2 hours. The B-type viscosity value at 25 ° C. at that time is assumed to be 100,
It is represented by the viscosity change rate after standing for a time. Δ: Change rate of less than 15%, good coating workability Δ: Change rate of 15 to 50%, slightly lacking in coating workability X: Change exceeding 50%, remarkable in coating workability Lack

(80 to 100 ° C. of B-staged composition)
E-type viscosity characteristics) The liquid crystal sealant composition of each example was applied to a smooth release film to a thickness of 10 to 50 μm, and the B-staged composition mass 0.6 obtained under the B-stage condition of each example was obtained. E-type viscometer (cone cup viscometer)
At a constant rate of 1 ° C./2 minutes from 40 ° C. to 120 ° C.
Up to (temperature)-(0.5 rpm rotational viscosity). The 90 ° C. viscosity was determined from the viscosity curve. × (−): 90 ° C. viscosity is less than 5 Pa · s Δ: 90 ° C. viscosity is 5 to 300 Pa · s ：: 90 ° C. viscosity is 301 to 1000 Pa · s × (+): 90 ° C. viscosity exceeds 1000 Pa · s

(Moisture Permeability Characteristics) The liquid crystal sealant composition of each example was applied on a smooth release film to a thickness of 70 to 120 μm, heat-treated at 80 ° C. for 30 minutes, and further thermally cured at 150 ° C. for 90 minutes. The cured film obtained as described above was cut out and subjected to a moisture permeability test in accordance with JIS-Z-0208, a moisture permeability test method for a moisture-proof packaging material of Japanese Industrial Standards (JIS), at 24 ° C at 60 ° C and 80 ° C. Thickness 10 permeated with time
Water vapor amount per 0 μm (unit: g / m ² · 24 hr
s) was determined. ◎: The moisture permeability of 60 ° C. is less than 35 g / m ² · 24 hrs, and the composition for a liquid crystal display cell sealant is particularly excellent in low moisture permeability. 〇: The moisture permeability of 60 ° C. is 35 to 80 g / m ² · 24 h.
rs, the composition for a liquid crystal display cell sealing agent is excellent in low moisture permeability. Δ: The moisture permeability property at 60 ° C. is 81 to 150 g / m ² · 24.
hrs, the low moisture permeability of the composition for a liquid crystal display cell sealant is considerably low. ×: The moisture permeability at 60 ° C. is 151 to 250 g / m ² · 2.
At 4 hrs, the composition for sealing a liquid crystal display cell slightly lacks low moisture permeability. XX: The moisture permeability at 60 ° C. is 251 g / m ² · 24 hrs.
Above, the liquid crystal sealant composition lacks low moisture permeability

Regarding the moisture permeability at 80 ° C., ◎: The moisture permeability at 80 ° C. is 100 g / m ² · 24 hrs or less, and the composition for a liquid crystal display cell sealant is particularly excellent in low moisture permeability. There 101 to 150g / m ² · ²
In 4hrs, a liquid crystal display cell seal agent for a composition excellent in low moisture permeability △: 80 ° C. The moisture permeability properties 151 to 200g / m ² · ²
In 4hrs, low moisture permeability is much lower × liquid crystal display cell seal composition for: 80 ° C. The moisture permeability properties 201 to 350g / m ² · ²
In 4hrs, a liquid crystal display cell seal composition is somewhat lacking in low moisture permeability ××: 80 ° C. The moisture permeability properties 351g / m ² · 24hrs
Above, the liquid crystal sealant composition lacks low moisture permeability

(Coefficient of linear expansion of cured product) The liquid crystal sealant composition of each example was coated on a smooth release film to a thickness of 70 to 120.
μ, heat-treated at 80 ° C. for 30 minutes, and heat-cured at 150 ° C. for 90 minutes to obtain a small piece of cured film (15 mm
Corner) was cut out, and the cured product was subjected to TMA measurement from 30 ° C. to 180 ° C. at a rate of 5 ° C./min. The linear expansion coefficient per 1 ° C. was determined by dividing the amount of strain from 30 ° C. to 80 ° C. by 50.

(Heat Deformation Temperature of Cured Body) The liquid crystal sealant composition of each example was coated on a smooth release film to a thickness of 70 to 120.
μ, heat-treated at 80 ° C. for 30 minutes, and heat-cured at 150 ° C. for 90 minutes to obtain a small piece of cured film (15 mm
Corner) was cut out, and the cured product was subjected to TMA measurement from 40 ° C. to 180 ° C. at a rate of 5 ° C./min. The inflection point of the amount of distortion was defined as the heat distortion temperature (Tg) of the cured product.

(Water Absorption of Cured Body) The liquid crystal sealant composition of each example was coated on a smooth release film to a thickness of 70 to 120 μm, and heat-treated at 80 ° C. for 30 minutes.
A cured film obtained by heat-curing is cut out into a 100 mm square, and the cured body is immersed in boiling water for 30 minutes, 3 hours or 5 hours to determine the weight increase, and the value is divided by the original mass. Multiplied by 100 was taken as the water absorption. That is, water absorption (%) = (mass increase after boiling water immersion / mass before test) × 100.

(Hardness of Cured Body) The liquid crystal sealant composition of each example was heat-treated on a smooth release film under vacuum at 80 ° C. for 30 minutes, and then the composition was placed in a 1 cm square, 2 mm high aluminum cell. And cured by heating at 150 ° C. for 90 minutes. The surface hardness of the cured product was measured at room temperature 23 ° C. using a Shore D hardness meter. ：: Shore D hardness is 80 or more and excellent in rigidity 〇: Shore D hardness is 70 or more and less than 80 and the cured product is rich in rigidity X: Shore D hardness is less than 70 and lacks in rigidity

(Storage Elastic Modulus of Cured Body) The liquid crystal sealant composition of each example was coated on a smooth release film to a thickness of 70 to 120.
μ, and heat-treated at 80 ° C. for 30 minutes, and then heat-cured at 150 ° C. for 90 minutes to cut out a cured film obtained by cutting into a 100 mm square. 5 Hz per minute in a frequency of 1 Hz, air atmosphere
After obtaining a viscoelastic curve by heating at a constant speed in
The storage modulus in the 0 ° C. region was determined. 〇: Storage elastic modulus of 1 × 10 ⁵ Pa to 1 × 10 ⁸ Pa ×: Storage elastic modulus of 9.9 × 10 ⁴ Pa or less

(Free Ion Concentration) The ionic conductivity of an aqueous solution in which 100 parts by mass of the composition for a liquid crystal display cell sealing agent of each example and ultrapure water of the same mass were stirred and mixed at room temperature for 30 minutes was measured. ：: Conductivity is 2 mS / m or less 〇: 2.1 to 10 mS / m ×: 10.1 to 50 mS / m XX: 51 mS / m or more

(Joint Seal Test) A liquid crystal display cell manufactured by performing adhesive curing under the conditions shown in each example was magnified with a 20 × magnifying glass and observed with the naked eye to determine whether or not the seal line was disordered. The presence or absence of a defective seal due to the generation of a penetrating bubble was measured.

(Cell Wedge Peeling Test) A wedge is driven at 60 ° C. into a liquid crystal display cell manufactured through a single wafer press hardening process under the conditions shown in each example. It shows the adhesive strength of the sealant composition for display cells. ◎: Excellent in heat-resistant adhesiveness when the substrate is broken. 〇: Good cohesive failure of the composition for a liquid crystal display cell sealing agent, and good heat-resistant adhesiveness. X: When destruction with interfacial peeling is observed. Has a problem with heat resistant adhesive strength

(Wedge peeling test of cell after pressure cooker test) A liquid crystal display cell manufactured through a sheet-fed press hardening process under the conditions shown in each example was heated at 121 ° C.
After being exposed to a pressure cooker tester for 2 hours, it was taken out, and a wedge was driven in at normal temperature. ◎: Excellent in heat-resistant adhesiveness when the substrate is broken. 〇: Good cohesive failure of the composition for a liquid crystal display cell sealing agent, and good heat-resistant adhesiveness. X: When destruction with interfacial peeling is observed. Has a problem with heat resistant adhesive strength

(Non-leaking property of composition for liquid crystal sealant)
In the liquid crystal display cell manufactured through the single-wafer press hardening process under the conditions shown in each example, the threshold voltage of the liquid crystal is 1.38 volts from the liquid crystal filling port, and Δε of the liquid crystal is 12.4. After encapsulating an RC4087 liquid crystal material [manufactured by Chisso Corporation] by a vacuum method, the encapsulation opening is provided by Stract Bond ES-302.
[Mitsui Chemicals Co., Ltd.] sealed, and a polarizing plate was attached to the front side, and a polarizing plate with a reflecting plate was attached to the rear side.
After that, a drive circuit and the like were mounted on the unit to produce a liquid crystal panel. The non-bleeding property was evaluated based on whether or not the liquid crystal display function near the sealant of the liquid crystal panel normally functioned from the beginning of driving. 〇: When the liquid crystal display function can be exerted up to the time of sealing, non-bleeding property is secured. △: When liquid crystal display is not performed normally within 1 mm in the vicinity of the sealing, slightly lacking in bleeding property ×: Abnormality of the display function is seen beyond 1.1 mm in the vicinity of the seal, and the non-bleeding property is remarkably lacking.

(Seal Function Durability Test) An RC4087 liquid crystal material (manufactured by Chisso Corporation) was supplied from a liquid crystal filling port to a liquid crystal display cell manufactured through a single wafer press hardening process under the conditions shown in each example. The liquid was injected, and the sealing port was sealed with Struct Bond ES-302 (manufactured by Mitsui Chemicals, Inc.) to produce a liquid crystal panel. The liquid crystal panel is 65 ℃ / RH95%
Under the atmosphere of 250 hours, 500 hours, 1,000 hours
After being left for each time, the plate was taken out, a deflection plate was attached to the front side, and a deflection plate with a reflection plate was attached to the rear side.
Thereafter, a drive circuit and the like were mounted on the unit, and changes in the display function were observed. ：: No display unevenness was observed. 〇: Display unevenness was 15 at the distance from the sealing area around the cell.
Slightly observed within 0 μm Δ: display unevenness at distance from sealing around cell periphery of 15
X: when the display unevenness is 500 μm or more at the time of sealing and the display function is significantly reduced.

(Curing Start Temperature) 10 mg of the composition for a liquid crystal display cell sealant of each example was subjected to differential scanning calorimetry under atmospheric pressure (D
SC), the temperature at which the exothermic peak starts to change was determined as the curing start temperature from the differential heat curve obtained by raising the temperature at a constant rate of 5 ° C. per minute from 30 ° C. to 220 ° C.

(Curing Exothermic Peak Temperature) 10 mg of the composition for a liquid crystal display cell sealant of each example was heated at a constant rate of 5 ° C./min from 30 ° C. to 220 ° C. by differential scanning calorimetry (DSC) under atmospheric pressure. The maximum exothermic peak inflection point was determined as the maximum exothermic peak temperature from the obtained differential heat curve.

(Effect of Cured Body on Liquid Crystal) The liquid crystal sealant composition of each example was coated on a smooth release film to a thickness of 70 to 120 μm, and heat-treated at 80 ° C. for 30 minutes.
0.1 parts by mass of a cured film piece obtained by heat curing at 0 ° C. for 90 minutes was measured and taken in a closed glass container.
7 Add 1 part by mass of a liquid crystal material [manufactured by Chisso Corporation], seal under nitrogen atmosphere, heat the whole container at 125 ° C for 1 hour, take out the contents, and suck out the contents with a syringe equipped with a small ceramic filter. The liquid crystal is sampled, the specific resistance of the liquid crystal is measured by a specific resistance measuring instrument, and the measured value is represented by the amount of change from the specific resistance obtained by the test using only the liquid crystal (referred to as the original liquid crystal specific resistance). ：: change less than 50 times the original liquid crystal specific resistance 〇: cured product of the composition for a liquid crystal display cell sealant when there is a change of 50 to 250 times the original liquid crystal specific resistance Has a very small effect on the liquid crystal. ×: A change of 251 times or more from the original liquid crystal specific resistance is observed. The effect of the cured product of the liquid crystal display cell sealant composition on the liquid crystal is relatively large.

Raw Materials Used Epoxy resin (1) The monofunctional epoxy resin has an ionic conductivity of 1.5 mS (hereinafter simply referred to as the ionic conductivity of extracted water) of extracted water separated and extracted by contact mixing with pure water of the same mass for 1 hour. / M
(15 μS / cm) 2-ethylhexyl monoglycidyl ether (abbreviation: 2EHMG) purified to not more than 1.2 mS / m (12 μS / c)
m) t-Butylphenol monoglycidyl ether (abbreviation: t-BPMG) purified to the following was prepared.

As the polyfunctional epoxy resin having two or more functionalities, the following were used. As the bifunctional aliphatic epoxy resin, the ionic conductivity of the extraction water is 0.2 mS / m (2 μm).
1,6-hexanediol diglycidyl ether (abbreviated symbol: 1,6-HGDE) purified to S / cm) as a bifunctional bisphenol A type epoxy resin, a product of Mitsui Chemicals, Inc. “-140P” (average molecular weight 370), Yuka Shell Co., Ltd. product name “Epicoat 1007” (average molecular weight 4000), Mitsui Chemicals product name “Epomic R367” (average molecular weight 2600), and As a bifunctional bisphenol F type epoxy resin, Dainippon Ink Co., Ltd. product name "Epiclon 830-S" (average molecular weight of about 350 to 3)
70) was selected and used as a bifunctional hydrogenated bisphenol A type epoxy resin, product name "Epototo ST-1000" (average molecular weight 400 to 440) manufactured by Toto Kasei Co., Ltd. As a trifunctional novolak epoxy resin,
Product name of Toto Kasei Co., Ltd. "Epototo YDCN"
(Polystyrene equivalent weight average molecular weight of about 10 by GPC
00) as a triphenolethane-type epoxy resin, “EPOMIC VG3101” manufactured by Mitsui Chemicals, Inc.
As a trifunctional aminoepoxy resin, Sumitomo Chemical Co., Ltd. product "Sumika ELM-100", and as a tetrafunctional aminoepoxy resin, Toto Kasei Co., Ltd. product / product name "Epototo YH-434" ( The weight average molecular weight in terms of polystyrene by GPC was about 460). Also,
As the modified epoxy resin, a resin composition (abbreviated as EPA-005) obtained in Synthesis Example 6 below was used.

[0274] 2. Curing agent (2) As the phenol novolak resin, a product made by Mitsui Chemicals, Inc., trade name "Mirex VR9315" (resin having a phenol nucleus bonded by methylene), particularly a softening point temperature of 1
14.9 ° C., a free phenol content of 0.03% or less, a chlorine atom content of 0.01% or less, and an ionic conductivity of extraction water of 0.5 mS / m (5 μS / cm) were selected and used. (In the following examples, this resin is simply referred to as FP resin). As another phenol novolak resin, Novolak PSM-4261 manufactured by Gunei Chemical Co., Ltd., and as esterified phenol novolak resin, Novolak PSM-42 manufactured by Gunei Chemical Co., Ltd.
A resin in which 98 mol% of the phenolic hydroxyl group of No. 61 was benzoyl-esterified (hereinafter referred to as esterified PSM-4261) was prepared.

Further, all the esterified modified products shown below were obtained by the esterification modified according to Synthesis Example 1. However, the esterified trisphenol monomer, which is a high melting point substance, was produced according to Synthesis Example 2. Examples of the phenol aralkyl resin include “Xyloc XLC-225L” (a resin in which a phenol nucleus is bonded to a p-xylene nucleus via a methylene bond) manufactured by Mitsui Chemicals, Inc.
In particular, the weight average molecular weight in terms of polystyrene by GPC is 7150, the softening point is 84 ° C., and the free phenol is 0.0
1% or less, a chlorine atom content of 0.01% or less, and an extraction water having an ion conductivity of 0.3 mS / m (3 μS / cm) were selected and used (hereinafter simply referred to as XP resin). ).

Another phenol aralkyl resin includes:
A phenol nucleus is bonded to a p-xylene nucleus via a methylene bond, has a polystyrene-equivalent weight average molecular weight of about 1750, a softening point of 76 ° C., free phenol of 0.01% or less, and a chlorine atom content of 0. 01% or less,
The ionic conductivity of the extraction water is 0.3 mS / m (3 μS / c
m) (hereinafter simply referred to as XLP resin), and as its esterified phenol aralkyl resin,
A resin having an ion conductivity of 1.1 mS / m (11 μS / cm) (hereinafter simply referred to as an esterified aralkyl resin) is prepared by benzoyl esterifying 99 mol% of the active phenolic hydroxyl groups of the XLP resin. did. The alicyclic compound-modified phenol novolak resin has a mass average molecular weight in terms of polystyrene derived from purified phenol and α, α-dimethyl ether-2,5-dicyclopentadiene of 969, and an ion conductivity of the extracted water of 0. So-called dicyclopentadiene-modified phenol novolak resin (hereinafter simply referred to as DCN resin) or polystyrene equivalent derived from phenol and α, α-dimethyl ether-p-cyclohexane, which is 0.7 mS / m (7 μS / cm). Weight average molecular weight is 1084
And the ionic conductivity of the extracted water is 1 mS / m (10 μS
/ Cm), a so-called cyclohexane-modified phenol novolak resin (hereinafter simply referred to as CHN resin)
As the esterified alicyclic compound-modified phenol novolak resin, 91 mol% of the active phenolic hydroxyl groups in the dicyclopentadiene-modified phenol novolak resin were benzoyl-esterified, and the ion conductivity of the extracted water was 1 mS / m (10 μS / Cm) (hereinafter simply referred to as esterified DCN resin) or 100 mol% of the active phenolic hydroxyl groups in the cyclohexane-modified phenol novolak resin is benzoyl-esterified, and the ion conductivity of the extracted water is 0%. 0.6 mS / m (6
μS / cm) (hereinafter simply referred to as esterified CHN).
(Referred to as resin).

As the polycyclic aromatic compound-modified novolak resin, FPI-5136 manufactured by Kashima Oil Co., Ltd. (softening point: 75 ° C., number average molecular weight: 640, free phenol content: 0.1% or less, ionic conductivity of extracted water 0.8mS / m
(8 μS / cm)) and its esterified polycyclic aromatic compound-modified novolak resin is FPI-5136
95 mol% of the active phenolic hydroxyl groups of phenol was converted to benzoyl ester, and the ionic conductivity of the extracted water was 0.6 mS /
m (6 μS / cm) (hereinafter simply referred to as esterified FPI resin), and as a naphthol novolak resin, the mass average molecular weight in terms of polystyrene derived from β-naphthol and formaldehyde is 878, and the ion of the extracted water is A resin having a conductivity of 0.3 mS / m (3 μS / cm) (hereinafter simply referred to as an NN resin) was used as an esterified naphthol novolak resin in which 50 mol% of phenolic hydroxyl groups of the NN resin was benzoyl esterified. Esterified NN resins were each prepared.

As the naphthol aralkyl resin, β-
The polystyrene equivalent weight average molecular weight derived from naphthol and α, α-dimethyl ether-p-xylylene is 555, and the ionic conductivity of the extracted water is 0.7 mS / m.
(7 μS / cm) resin (hereinafter simply referred to as “NA resin”), and as the esterified naphthol aralkyl resin, an esterified NA resin in which 50 mol% of the phenolic hydroxyl groups of the NA resin is benzoyl-esterified is prepared. did.

As the alicyclic compound-modified naphthol novolak resin, the mass average molecular weight in terms of polystyrene derived from β-naphthol and α, α-dimethyl ether-2,5-dicyclopentadiene is 1240, and the ion conductivity of the extracted water is as follows. A resin having a degree of 0.7 mS / m (7 μS / cm) (hereinafter simply referred to as “DC-NN resin”) is an ester obtained by subjecting 50 mol% of phenolic hydroxyl groups of the DC-NN resin to benzoyl esterification. Chemical DC
-NN resin was prepared.

As the polyhydric phenol monomer, 4,4 '-[(2-hydroxyphenyl) methylene] bis [2,2] purified to an ionic conductivity of extracted water of 0.3 mS / m (3 μS / cm) 3,6-trimethylphenol] (hereinafter simply referred to as Tris-P compound) having a maximum particle size of 4 μm or less (pulverized by a laser irradiation type particle size distribution measuring method at a wavelength of 632.8 nm) by a pulverizer. 99.9% of the product curve with a maximum particle diameter of 4 μm or less).

As the esterified polyhydric phenol monomer, 99.3 mol% of the active phenolic hydroxyl group of the Tris P compound was benzoyl-esterified according to Synthesis Example 2, and the ion conductivity of the extracted water was 0%. .6mS / m
(6 μS / cm), hereinafter simply referred to as esterified tris P compound.

As another polycyclic aromatic compound-modified phenol novolak resin, Kashima Oil Co., Ltd. product name “P
PF resin; FPI-5127 (resin in which a phenol nucleus and a 3 to 4 ring polycyclic aromatic hydrocarbon nucleus derived from a light fraction from a catalytic cracking plant are randomly bonded by a methylene bond), and a free phenol content. 0.01% or less, a softening point of 80 ° C., a number average molecular weight in terms of polystyrene by GPC of about 650, and an ionic conductivity of the extraction water of 2 mS / m (20
μS / cm) or less.

As polyvinyl phenols, Maruzalinka M (S-
2)), the ionic conductivity of the extraction water is 2 mS / m (20
μS / cm) or less, as a polyvinylphenol copolymer, a product of Maruzen Petrochemical Co., Ltd., product name “Marcalinker CBA” (a random copolymer of pvinylphenol and butyl acrylate, The mass average molecular weight is 10,000) and the ionic conductivity of the extracted water is 2
A polyisopropenylphenol having a molecular weight of not more than mS / m (20 μS / cm) is a homopolymer of p-isopropenylphenol and has a weight average molecular weight by GPC of 3350 and an ion conductivity of 2 mS / m (20
μS / cm) or less (hereinafter simply referred to as OP resin)
Was prepared. As the polyisopropenyl phenol copolymer, Mitsui Chemicals, Inc. product / trade name “Mirex SP” (a random copolymer of p-isopropenyl phenol and styrene, having a polystyrene-equivalent weight average molecular weight of about 4000), those having an ion conductivity of 2 mS / m (20 μS / cm) or less were selected and prepared.

As the dihydrazide compound, adipic dihydrazide (abbreviation: ADH) was selected. As the imidazole-epoxy resin adduct-type latent epoxy curing agent, "CatZ-15" manufactured by Mitsui Chemicals, Inc. or "Amicure PN23" manufactured by Ajinomoto was selected and used.

Synthesis Example 1 Production of Esterified Novolak Resin A phenol novolak resin (trade name) was placed in a glass container equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser.
107 g of PSM-4216, hydroxyl equivalent 107 g / eq (manufactured by Gunei Chemical Co., Ltd.) were charged, and the internal temperature was raised to 125 ° C. While maintaining the internal temperature at the same temperature, 140.6 g of benzoyl chloride was added dropwise over 2 hours while stirring. Then, 12
After performing the reaction for 2 hours while maintaining the temperature at 5 ° C, the temperature was further increased to 140 ° C.
Temperature. After aging for 2 hours at 140 to 150 ° C, the generated hydrochloric acid gas is changed to a maximum of 150 ° C / 10 mmHg.
The solvent was distilled off under reduced pressure. The resin obtained here is dissolved in 1000 g of toluene, washed with hot water at 60 to 70 ° C. until the waste water becomes neutral, and then toluene is removed up to 150 g.
210 g of a so-called esterified phenol novolak resin (esterified PSM-4216) in which 98 mol% of the hydroxyl groups were distilled off by distillation at a temperature of 5 ° C./5 mmHg.
I got

Synthesis Example 2 Production of Esterified Trisphenol Compound In a glass container equipped with a thermometer, stirrer, dropping funnel and reflux condenser, 4,4 ′-[(2-hydroxyphenyl) methylene] bis [2 , 3,6-trimethylphenol] and 100 parts of acetophenone, and the internal temperature was raised to 125 ° C. With the internal temperature kept at the same temperature, 126.5 g of benzoyl chloride was added dropwise over 2 hours while stirring. Thereafter, the reaction was performed for 2 hours while maintaining the temperature at 125 ° C., and the temperature was further increased to 140 ° C. 140 to 150
After aging for 2 hours at ℃, the generated hydrochloric acid gas
The solvent was distilled off under reduced pressure at 50 ° C./10 mmHg. The compound obtained here is dropped into 1000 g of toluene to precipitate, and the obtained crystal component is dissolved again in a 5% water-acetone mixed solution, and the precipitation is repeated 5 times with a toluene solvent. After recrystallizing the crystals until they become acidic, the crystals were dried at a maximum of 150 ° C./5 mmHg to obtain a so-called esterified trisphenol monomer (ester) having 99.3 mol% of hydroxyl groups benzoylated. (Trisphenol compound).

[0287] 3. Curing accelerator (3) 3-P-chlorophenyl-1, having a purity of 99.7%,
1-dimethylurea (hereinafter abbreviated as accelerator U), 2,
As 4- [bis (1,1-dimethylurea)] toluene, Ucat-3502T (hereinafter simply abbreviated as 3502T) manufactured by San Apro Co., Ltd., 3,5-di (1,1-dimethylurea) -5-methyl- 2-cyclohexene-1-
Turn on the product Ucat-3503N manufactured by San Apro
(Hereinafter simply referred to as 3503N), 2-ethyl-4
-As methylimidazole, 2E4MZ and triphenylphosphine (reagent) manufactured by Shikoku Chemicals Co., Ltd. are prepared, and the maximum particle diameter is 4 μm or less by a pulverizer (laser irradiation type particle diameter distribution of 632.8 nm wavelength). The maximum particle diameter of 99.9% of the weighted product curve obtained by the measurement method and 4 μm or less) was used.

[0288] Also, Journal of generator
al chemistry of USSR, 5
5, a curing accelerator represented by the following general formula (13) [Chemical Formula 16] (hereinafter simply referred to as PZO) was used according to the production method described in p. 1453 (1985).

[0289]

Embedded image

[0290] 4. Inorganic filler (5) As spherical silica, 6% by mass of γ-glycidoxypropyltrimethoxysilane dry-processed filler manufactured by Tatsumori Co., Ltd. and having a trade name of “Admafine SO-E1” (hereinafter simply referred to as SO-E)
1-6) as spherical alumina, 5% by mass of γ-glycidoxypropyltrimethoxysilane dry-processed filler (trade name: ADMAFINE SO-A800, manufactured by Tatsumori Co., Ltd.) (hereinafter simply referred to as SO-A805). ) As amorphous silica, product name “Aerosil # 200” (trade name: 0.08 μm of primary average particle size obtained by electron microscopy), product name and product name of Nippon Aerosil Industry Co., Ltd. The name “MU-120” (primary primary average particle size 0.07 μm determined by electron microscopy) was
Showa Denko Co., Ltd. product name "UA-5105" (hereinafter simply referred to as "amorphous alumina 1") as titanium oxide and Ishihara Sangyo Co., Ltd. product name "CR-EL" as titanium oxide. (50% of the weighted product curve obtained by a laser irradiation type particle size distribution measuring method of 632.8 nm wavelength)
1μ in average size with particle size as primary average particle size
m) were each used.

The following materials were used as the grafted modified alumina. As the grafted modified alumina, 6
Amorphous γ having a 50% average particle size of 0.1 μm and a 99.5% particle size of 2 μm obtained from a weighted product curve obtained by a laser irradiation type particle size distribution measuring method at a wavelength of 32.8 nm.
-Alumina was prepared, and 1 kg of the amorphous γ-alumina was added to 30.3 of γ-glycidoxypropyltrimethoxysilane (product name: KBM403, product of Shin-Etsu Chemical Co., Ltd.).
g in a 100 ° C. atmosphere.
Aged at 48 ° C. for 48 hours was used (hereinafter simply referred to as grafted modified alumina). The dried sample after washing 10 parts of the grafted modified alumina with 100 parts of toluene solvent five times also had a 1.7% loss on heating as an organic component when the dried sample was baked in a crucible. It was found that about 2.4% of γ-glycidoxypropyltrimethyxisilane was grafted.

[0292] 5. Coupling agent (6) γ-glycidoxypropyltrimethoxysilane (hereinafter, referred to as
N-phenyl-γ-aminopropyltrimethoxysilane (hereinafter simply referred to as aminosilane) and γ-isocyanatopropyltriethoxysilane (hereinafter simply referred to as isocyanatosilane) were selected and used.

[0293] 6. As the rubber-like polymer fine particles (4), the compositions prepared through the following Synthesis Examples 3 and 4 were used.

Synthesis Example 3 Rubber-like polymer fine particles (finely crosslinked acrylic rubber fine particles;
Synthesis of epoxy resin composition (a) containing abbreviated as S1) 2000 equipped with a stirrer, gas inlet tube, thermometer, and cooling tube
Bisphenol F type epoxy resin (Epiclon 830) as a bifunctional epoxy resin
S. Dainippon Ink and Chemicals, Inc. (600 g), acrylic acid (12 g), dimethylethanolamine (1 g), and toluene (50 g) were added, and the mixture was reacted at 110 ° C. for 5 hours while introducing air to introduce a double bond. Next, 350 g of butyl acrylate, 20 g of glycidyl methacrylate, 1 g of divinylbenzene, 1 g of azobisdimethylvaleronitrile and 2 g of azobisisobutyronitrile were added, and the mixture was reacted at 70 ° C. for 3 hours while introducing nitrogen into the reaction system. 90
The reaction was carried out at a temperature of 1 hour. Subsequently, toluene is removed under reduced pressure of 110 ° C., the composition is rapidly cured at a low temperature in the presence of a photocuring catalyst, and the fracture surface morphology of the cured product is observed with an electron microscope to reduce the dispersed rubber particle diameter. An epoxy resin composition (a) in which finely-crosslinked acrylic rubber fine particles (S1) having a minimum particle size of 0.02 μm and a maximum particle size of 1 μm obtained by the measurement method were uniformly dispersed was obtained. The content of finely crosslinked acrylic rubber fine particles (S1) calculated from the charged monomer amount and the residual monomer was found to be 37.9% by weight. The softening point temperature of the finely crosslinked acrylic rubber fine particles (S1) determined by subjecting the epoxy resin composition (a) to TBA was -42 ° C.

Synthesis Example 4 Synthesis of Epoxy Resin Composition (b) Containing Silicon-Based Rubber-Like Polymer Fine Particles (Cross-Linked Silicon Rubber Fine Particles; S2) 2000 equipped with a stirrer, gas inlet tube, thermometer, and cooling tube
ml of a four-necked flask, and a bisphenol F type epoxy resin (Epiclon 8) is used as a bifunctional epoxy resin.
600 g (30S, manufactured by Dainippon Ink and Chemicals, Inc.), 12 g of acrylic acid, 1 g of dimethylethanolamine and 50 g of toluene were added, and the mixture was reacted at 110 ° C. for 5 hours while introducing air to introduce a double bond. Next, 5 g of hydroxy acrylate, 10 g of butyl acrylate and 1 g of azobisisobutyronitrile were added, reacted at 70 ° C. for 3 hours, and further reacted at 90 ° C. for 1 hour. Then 110 ° C
The toluene was removed under reduced pressure. Next, 70 g of a silicone intermediate having a methoxy group in the molecule and 0.3 g of dibutyltin dilaurate were added, the reaction was carried out at 150 ° C. for 1 hour, and the reaction was continued for another 1 hour to remove generated methanol. An epoxy resin composition in which finely crosslinked silicon rubber fine particles (S2) are uniformly dispersed is added with 300 g of a 1/1 mixture of room temperature-curable two-liquid type silicone rubber mixed in 1/1 with this graft, and reacted for 2 hours. b) was obtained.

The composition (b) was rapidly cured at a low temperature in the presence of a photo-curing catalyst, and the average morphology obtained by observing the fracture surface morphology of the cured product with an electron microscope and measuring the dispersed rubber particle diameter was obtained. This is an epoxy resin composition (b) in which finely-crosslinked silicon rubber fine particles (S2) having a particle diameter of 1.5 μm are uniformly dispersed. Further, the content of finely-crosslinked silicon rubber fine particles (S2) calculated from the charged amount is 30.0%.
Further, the softening point temperature of the finely crosslinked silicone rubber fine particles (S2) determined by subjecting the epoxy resin composition (b) to TBA was -65 ° C.

[0297] 7. As the high softening point polymer fine particles (8), the composition prepared in Synthesis Example 5 shown below was used. Synthesis Example 5 Synthesis of High Softening Point Acrylic Polymer Fine Particles (P1) 20 equipped with a stirrer, gas inlet tube, thermometer, and reflux cooling tube
420.5 ion-exchanged water in a 00 ml four-necked flask
g, itaconic acid 10 g, and sodium alkyldiphenyl ether disulfonate as a surfactant.
2.6 g of Kao's “Perex SS-L” was added, and the temperature was raised to 70 ° C. while introducing nitrogen. At the same temperature, 1.2 g of potassium persulfate was added to ion-exchanged water 10
g of an aqueous initiator solution dissolved therein, and further added with 5 g of n-butyl acrylate and 5 g of methyl methacrylate.
g of hydroxyethyl methacrylate and 0.5 g of hydroxyethyl methacrylate were added all at once, and seed polymerization was performed at 70 ° C. for 20 minutes. Thereafter, under the same temperature atmosphere, a mixed monomer liquid of 339 g of methyl methacrylate, 20 g of glycidyl methacrylate, 40 g of n-butyl acrylate, and 2 g of 1,6-hexanediol dimethacrylate was added to 160 g of ion-exchanged water and the above-mentioned “Perex SS-L” was added. An emulsified solution mechanically emulsified with an aqueous solution containing 1.8 g was dropped continuously over about 4 hours. After the completion of the dropping, the polymerization of the remaining monomer was further completed at the same temperature for 1 hour, and the solid content was 39.9% by weight.
(Em-1) was obtained. Subsequently, the (Em-1) solution was subjected to an ultrafiltration apparatus using pure water for 48 hours to remove and purify water-soluble components. 1000 g of the Em-1 emulsion solution after the ultrafiltration treatment was applied to a spray dryer to obtain 388 g of high softening point acrylic polymer fine particles (P1) having a water content of 0.1% or less.

[0298] The average primary particle size of the dispersed particles obtained by using Em-1 under an electron microscope was 170 nm.
(0.17 μm). The fine cross-linking degree index of the high softening point acrylic polymer fine particles (P1) has a fine cross-linking degree of 0.5% by mass in terms of the content ratio of the cross-linkable monomer in all the monomers. From the TBA information using the hot-melt film, the softening point temperature of the high softening point acrylic polymer fine particles (P1) was 80 ° C.

Synthesis Example 6 42 parts of Epototh YDCN and 13 of Epicron 830S
3 parts and 250 parts of toluene as a solvent were previously added to 500 parts.
A polydimethylsiloxane having a primary amino group at both terminals and having an amine value of 1500 was charged into a reaction flask having a capacity of 1 ml and was stirred under stirring (product of Shin-Etsu Silicon Co .; X-22-161B).
After adding 100 parts and reacting at 120 ° C. for 2 hours, the solvent was removed under reduced pressure at the same temperature to obtain 275 parts of a modified epoxy resin. This modified epoxy resin composition is called EPA-005.

[0300] 8. Composite particles having rubber-like polymer fine particles (4) as core phase and high softening point polymer fine particles (8) as shell phase Rubber-like polymer fine particles (4) as core phase and high softening point polymer fine particles (8) as shell phase Zeon Chemical Co., Ltd. product “Zeon F351” (average particle diameter 0.3 μm) known as a composite particle having a core-shell mass ratio of 1: 1.
m) was obtained, and a 50% aqueous solution thereof was deionized in an ultrafilter using pure water for 48 hours, and then powdered with a spray dryer was used. Hereinafter, it is simply referred to as “high softening point polymer fine particles P2”.

Example 1 An epoxy resin composition obtained by dissolving 4.1 parts of a solid epoxy resin, cresol novolac type epoxy resin “Epototo YDCN” in 5 parts of methyl carbitol, and having an average particle diameter of 0.05 μm was used. Epoxy resin composition (a) 2 in which finely-crosslinked acrylic rubber fine particles (S1) are uniformly dispersed
6.8 parts, 13.3 parts of esterified PSM4261 (benzoylated novolak resin) as a curing agent and XLP resin (Mirex XL-2 which is a phenol aralkyl resin)
L) 28.3 parts of a curing agent solution in which 11.3 parts were previously dissolved in 13.7 parts of methyl carbitol, and P was used as a curing accelerator.
ZO1.5 parts, amorphous silica "MU-120" 2.1
Parts, 20.6 parts of spherical silica “SO-E1-6” and 1.6 parts of KBM403 as a coupling agent are mixed at once, and preliminarily kneaded with a Dalton mixer. The kneaded material obtained by kneading was vacuum defoamed to obtain a composition for a liquid crystal display cell sealant (E1).
I got The composition for liquid crystal display cell sealant (E1) has an epoxy resin content of 20.7%, a rubber-like polymer fine particle content of 10.2%, and an inorganic filler content of 22.7.
%, Solvent content 18.7%, coupling agent content 1.
6%, curing agent content 24.6%, curing accelerator content 1.
5%. Composition for liquid crystal display cell sealant (E
Table 2 shows the physical properties of the sealing agent relating to 1).

Liquid Crystal Display Cell Sealant Composition (E1) 1
Into 00 parts, 5 parts of a 5 μm-thick glass short fiber gap control agent (5 parts) was blended and mixed well, and then a composition obtained by first mixing a transparent electrode and an alignment film-treated glass substrate for a liquid crystal cell (hereinafter simply referred to as a “substrate”). On a substrate, a pattern consisting of a total of 4 cells (1 inch in cell size) is printed by screen on each of the top, bottom, left, and right, and the width of the sealant is about 20 to 22 μm. ITO consisting of
A substrate was obtained. Then, after treating with a 90 ° C. hot air drier for 15 minutes, another ITO substrate to be paired is placed, and after alignment, the plate is temporarily heated by rigid single-wafer press heating at a pressing pressure of 0.03 MPa / cm ² and 180 ° C./4 minutes. After bonding, the resultant was put into an oven heated to 150 ° C. for 90 minutes, and a bonding seal test for full-curing bonding was repeatedly performed 10 times. As a result, there was no sample with no defective seal or disturbance of the seal line due to the generation of a bubble penetrating the seal, and a desired liquid crystal display cell substrate could be manufactured in all lots. Next, after each cell was cut individually, a cell wedge peeling test and a sealing function durability test were performed.
It was shown to.

Example 2 According to the formulation shown in Table 1, in the same manner as in Example 1, a liquid crystal display cell sealant composition (E2) was obtained. The composition for liquid crystal display cell sealant (E2) has an epoxy resin content of 26.2% and a rubber-like polymer fine particle content of 6.5.
%, Inorganic filler content 16.5%, solvent content 19.
7%, coupling agent content 1.2%, curing agent content 2
8.4% and a curing accelerator content of 1.5%. Table 2 shows the physical properties of the liquid crystal display cell sealing composition (E2). Composition for liquid crystal display cell sealant (E
2) 5 parts of a glass short fiber gap control agent having a thickness of 5 μm is mixed with 100 parts, and a composition obtained by mixing well is first placed on an ITO substrate. A pattern having a cell size of 1 inch was screen-printed to obtain an ITO substrate having a width of about 0.5 mm and a sealant applied thickness of about 20 to 22 μm.
Then, after treating with an 80 ° C. hot air dryer for 30 minutes, another ITO substrate to be paired is placed, and after alignment, a rigid single-wafer press heating is performed at a pressing pressure of 0.03 MPa / cm ² at 180 ° C./4 minutes. After bonding, the resultant was placed in an oven heated to 150 ° C. for 90 minutes, and a bonding seal test for performing full-curing bonding was repeatedly performed 10 times. as a result,
There were no defective samples and no disturbance of the seal line due to the generation of bubbles penetrating the seal, and a desired liquid crystal display cell substrate could be manufactured in all lots. Next, each cell was cut individually and then subjected to a wedge pull-off test and a sealing function durability test of the cells. The results are shown in Table 2.

Example 3 According to the formulation shown in Table 1, a composition (E3) for a liquid crystal display cell sealing agent of the present invention was obtained in the same manner as in Example 1. The composition for liquid crystal display cell sealant (E3) has an epoxy resin content of 20.18%, a rubbery polymer fine particle content of 6.82%, an inorganic filler content of 22%, and a solvent content of 1.
5%, coupling agent content 1%, curing agent content
5%, and a curing accelerator content of 1.5%. Table 2 shows the physical properties of the liquid crystal display cell sealing composition (E3). Composition for liquid crystal display cell sealant (E3)
A composition obtained by adding 2 parts of a 6 μm short glass fiber gap control agent to 100 parts and thoroughly mixing the resulting mixture was first subjected to IT
On the O-substrate, a pattern consisting of a total of 4 cells (cell size of 1 inch), one for each of the top, bottom, left and right, is screen-printed on each O-substrate.
An ITO substrate of 0 to 22 μm was obtained. Then 9
After 15 minutes of heat treatment in a 5 ° C. hot air dryer, another I to be paired
Place the TO substrate on it and press
After temporary bonding by a rigid heat press heating method at Pa / cm ² , 170 ° C./5 minutes, the adhesive was further heated in a 150 ° C. heating oven for 8 minutes.
The bonding seal test of fully curing for 0 minutes was repeated 10 times. As a result, no defective seal or disturbance of the seal line was caused by the generation of bubbles penetrating the seal, and there was no sample, and a desired liquid crystal display cell substrate could be manufactured in all lots. Next, after each cell was cut individually, a cell wedge peeling test and a sealing function durability test were performed.
It was shown to.

Example 4 According to the formulation shown in Table 1, in the same manner as in Example 1, a liquid crystal display cell sealant composition (E4) was obtained. The composition for liquid crystal display cell sealant (E4) has an epoxy resin content of 21.3%, a rubbery polymer fine particle content of 10.4%, an inorganic filler content of 23.3%, and a solvent content of 17.4%. , A coupling agent content of 1.7%, a curing agent content of 24.3%, and a curing accelerator content of 1.6%. Table 2 shows the physical properties of the sealing composition for the liquid crystal display cell sealing composition (E4). To 100 parts of the composition for liquid crystal display cell sealant (E4), 2 parts of a gap control agent of 5 μm-thick short glass fiber was blended and thoroughly mixed. A screen consisting of a total of 4 cells (1 inch in cell size), each of which has a width of about 0.5 mm and a sealant coating thickness of about 22 to 24 μm.
A substrate was obtained. Then, after treating with a hot air dryer at 90 ° C. for 15 minutes, another ITO substrate to be paired is placed, and after alignment, a temporary press is performed by rigid single-sheet press heating at a pressing pressure of 0.03 MPa / cm ² and 180 ° C./4 minutes. After bonding, continue with 1
A bonding seal test in which the film was put into a heating oven at 50 ° C. for 90 minutes and fully cured and bonded was repeated 10 times. as a result,
There was no defective sample and no disturbance of the seal line due to the generation of the bubble penetrating the seal, and the desired liquid crystal display cell substrate could be manufactured in all lots. Next, each cell was cut individually and then subjected to a wedge pull-off test and a sealing function durability test of the cells. The results are shown in Table 2.

[0306]

[Table 1]

[0307]

[Table 2]

Example 5 An epoxy resin composition obtained by dissolving 20 parts of a cresol novolak type epoxy resin “Epototo YDCN” as a solid epoxy resin and 2 parts of a bisphenol A type epoxy resin “Epomic R367” in 9 parts of methyl carbitol was used. 15.5 parts of an epoxy resin composition (a) in which finely crosslinked acrylic rubber fine particles (S1) having an average particle diameter of 0.05 μm are uniformly dispersed, and 25 parts of an XP resin (phenol aralkyl resin) as a curing agent are methyl carbitol. 35 parts of a curing agent solution previously dissolved in 10 parts, 1 part of accelerator U as a curing accelerator, 2 parts of amorphous silica "MU-120", 14.6 parts of amorphous alumina "UA-5105", silane coupling agent And 0.9 parts of aminosilane at the same time, and premixed with a Dalton mixer. In kneaded until the solid material is 5μm or less, to obtain a kneaded product was vacuum defoamed Table 3 liquid crystal display cell seal agent composition according to (E5). The composition for a liquid crystal display cell sealant (E5) is composed of an epoxy resin having 3.5 epoxy groups in a molecule on an average weight basis, and has a content of 31.7.
3%, rubbery polymer fine particle content 5.87%, inorganic filler content 16.6%, solvent content 19%, silane coupling agent content 0.9%, hardener content 25%,
It consists of a curing accelerator content of 1%. Table 4 shows the physical properties of the liquid crystal display cell sealing composition (E5).

Liquid Crystal Display Cell Sealant Composition (E5) 1
5 parts of a glass short fiber gap control agent having a thickness of 5 μm was added to 00 parts, and the composition obtained by mixing well was first placed on an ITO substrate. A pattern having a cell size of 1 inch) was screen-printed to obtain an ITO substrate having a width of about 0.5 mm and a sealant applied thickness of about 20 to 22 μm.
Then, after treating with an 80 ° C. hot air drier for 30 minutes, another ITO substrate to be paired is placed, and after alignment, the plate is temporarily heated by a rigid single-wafer press heating at a pressing pressure of 0.03 MPa / cm ² and 180 ° C./4 minutes. After the bonding, a bonding seal test in which the resultant was put into a heating oven at 150 ° C. for 90 minutes and finally cured and bonded was repeated 10 times. As a result, defective seal locations and seal line disturbances due to the generation of bubbles
There was no sample, and a desired liquid crystal display cell substrate could be manufactured in all lots. Next, each cell was individually cut and then subjected to a cell wedge peeling test, a cell wedge peeling test after a 121 ° C./2 hour pressure cooker test, and a liquid crystal display function of the obtained cell was observed. Are also shown in Table 4. Table 4 also shows the results of the sealing function durability test performed using the obtained cells.

Example 6 According to the formulation shown in Table 3, in the same manner as in Example 5, a composition (E6) for a liquid crystal display cell sealant of the present invention was obtained. The composition for a liquid crystal display cell sealant (E6) is composed of an epoxy resin having three epoxy groups in one molecule on a mass average, and has a content of 29.2% and a rubber-like polymer fine particle content of 3.8%. 9.5 high softening point polymer fine particle content
%, Inorganic filler content 16%, solvent content 22%, silane coupling agent content 1.5%, curing agent content 16
% And a curing accelerator content of 2%. The initial viscosity at 25 ° C. measured by an E-type viscometer was 65 Pa · s. Table 4 shows the physical properties of the sealant related to the liquid crystal display cell sealant composition (E6). Composition for liquid crystal display cell sealant (E
6) 5 parts of a glass short fiber gap control agent having a thickness of 5 μm was blended with 100 parts of the mixture, and the composition obtained by sufficiently mixing the mixture was first placed on an ITO substrate. A pattern composed of cells (cell size is 1 inch) was screen-printed to obtain an ITO substrate having a width of about 0.5 mm and a sealant applied thickness of about 20 to 22 μm. Then, after another 15 minutes of treatment in a 90 ° C. hot air drier, another ITO substrate to be paired is placed, and after alignment, the plate is temporarily heated by a rigid single-sheet press at a pressing pressure of 0.03 MPa / cm ² and 180 ° C./4 minutes. After the bonding, a bonding seal test in which the resultant was put into a heating oven at 150 ° C. for 90 minutes and finally cured and bonded was repeated 10 times. As a result, defective seals and seal line disturbances due to the occurrence of seal penetration bubbles
There was no single sample, and the desired liquid crystal display cell substrate could be manufactured in all lots. Next, each cell was individually cut and then subjected to a cell wedge peeling test, a cell wedge peeling test after a 121 ° C./2 hour pressure cooker test, and a liquid crystal display function of the obtained cell was observed. Are also shown in Table 4. Table 4 also shows the results of the sealing function durability test performed using the obtained cells.

Example 7 [0311] Table 3 was obtained in the same manner as in Example 6, except that the high softening point polymer fine particles (P2) were replaced with the high softening point acrylic fine particles (P2). The composition (E7) for a liquid crystal display cell sealant described above was obtained. The composition for a liquid crystal display cell sealant (E7) is composed of an epoxy resin having three epoxy groups in a molecule in weight average, and has a content of 29.2% and a content of rubber-like polymer fine particles of 8.
55%, high softening point polymer fine particle content 4.75%, inorganic filler content 16%, solvent content 22%, silane coupling agent content 1.5%, curing agent content 16%, curing accelerator Content of 2%. The initial viscosity at 25 ° C. measured by an E-type viscometer was 68 Pa · s. Table 4 shows the physical properties of the liquid crystal display cell sealing composition (E7). Composition for liquid crystal display cell sealant (E7) 1
Then, 3 parts of a gap control agent of spherical silica having a particle diameter of 5 μm are mixed with 00 parts, and the composition obtained by mixing well is first placed on an ITO substrate. A pattern having a size of 1 inch was screen-printed to obtain an ITO substrate having a width of about 0.5 mm and a coating thickness of a sealant of about 20 to 22 μm.
Then, after 15 minutes of treatment in a hot air dryer at 80 ° C., another ITO substrate to be paired is placed, and after alignment, temporary bonding is performed by a vacuum single-wafer press heating method at −980 hPa, 150 ° C./10 minutes. Further, a bonding seal test in which the film was left to stand in a heating oven at 150 ° C. for 80 minutes and finally cured and bonded was repeatedly performed 10 times. As a result, there was no seal failure due to the generation of bubbles penetrating the seal, and a desired liquid crystal display cell substrate could be manufactured in all lots. Then, after each cell was cut individually, a wedge peeling test of the cell, 1
The cell was subjected to a wedge peeling test after the pressure cooker test at 21 ° C. for 2 hours, and the presence or absence of a defective seal penetration of the obtained cell and the linearity of the seal line were observed with a magnifying glass. It was shown to. Table 4 also shows the results of the sealing function durability test performed using the obtained cells.

Example 8 According to the formulation shown in Table 3, a composition (E8) for a liquid crystal display cell sealing agent of the present invention was obtained in the same manner as in Example 5. The composition for liquid crystal display cell sealant (E8) has an epoxy resin content of 35%, an inorganic filler content of 16.6%, a solvent content of 19%, and a silane coupling agent content of 0.9.
%, A curing agent content of 27.5%, and a curing accelerator content of 1%. The initial viscosity at 25 ° C. measured by an E-type viscometer was 3
It was 9 Pa · s. Table 4 shows the physical properties of the liquid crystal display cell sealing composition (E8). To 100 parts of the composition for liquid crystal display cell sealant (E8), 3 parts of a gap control agent of spherical silica having a particle diameter of 5 μm was blended and mixed thoroughly, and the composition obtained was first mixed on an ITO substrate per substrate. A pattern consisting of a total of 4 cells (1 inch in cell size) for each of the upper, lower, left and right sides was screen-printed to obtain an ITO substrate having a width of about 0.5 mm and a sealant applied thickness of about 20 to 22 μm. Then, after treating with a hot air dryer at 95 ° C. for 25 minutes, another ITO substrate to be paired is placed, and after positioning, a press pressure of 0.03 MPa / c is applied.
A bonding seal test was performed ten times, in which a temporary bonding was performed by heating a rigid single-wafer press at m ² , 165 ° C./5 minutes, and then left in a heating oven at 150 ° C. for 90 minutes to perform full-curing bonding. As a result, there was no seal failure due to the generation of bubbles penetrating the seal, and a desired liquid crystal display cell substrate could be manufactured in all lots. Next, each cell was cut individually, and then subjected to a cell wedge peeling test and a cell wedge peeling test after a 121 ° C./2 hour pressure cooker test. The linearity of the line was observed with a magnifying glass, and the results are shown in Table 4. Table 4 also shows the results of the sealing function durability test performed using the obtained cells.

[0313]

[Table 3]

[0314]

[Table 4]

Example 9 According to the formulation shown in Table 5, in the same manner as in Example 5, a composition for liquid crystal display cell sealant (E9) of the present invention was obtained. The composition for liquid crystal display cell sealant (E9) is composed of an epoxy resin having a weight average of 2.5 epoxy groups in one molecule, the content of which is 37%, the content of rubber-like polymer fine particles is 3.9%, Inorganic filler content 10.8%, high softening point polymer fine particle content 3.5%, silane coupling agent content 2%, curing agent content 16.6%, curing accelerator content 2.2%, It consists of a solvent content of 23% and a wax content of 1%. The initial viscosity at 25 ° C. measured with an E-type viscometer was 6
It was 4 Pa · s. Liquid crystal display cell sealant composition (E
Table 6 shows the physical properties of the sealant relating to 9).

Composition for Liquid Crystal Display Cell Sealant (E9) 1
Then, 3 parts of a spherical silica gap control agent having a particle size of 5 μm was blended with 00 parts, and a composition obtained by sufficiently mixing the resulting mixture was first placed on an ITO substrate. A pattern having a size of 1 inch was screen-printed to obtain an ITO substrate having a width of about 0.5 mm and a coating thickness of a sealant of about 20 to 22 μm.
Then, it is dried for 20 minutes in a hot air dryer at 90 ° C., another ITO substrate to be paired is placed thereon, and after alignment, the pressure is 0.05 MPa / cm ² and the temperature is 150 ° C./6 minutes. After the temporary bonding, the bonding seal test was further repeated 10 times in the heating oven at 150 ° C. for 80 minutes. As a result, there was no seal failure due to the generation of bubbles penetrating the seal, and a desired liquid crystal display cell substrate could be manufactured in all lots. Then, each cell was cut individually, and then the wedge-peeling test of the cells was performed.
The cell was subjected to a wedge peeling test after the pressure cooker test at 0 ° C./3 hours, and the presence or absence of defective seal penetration of the obtained cell and the linearity of the seal line were observed with a magnifying glass. The results are shown in Table 6. Was. Table 6 also shows the results of the sealing function durability test performed using the obtained cells.

Example 10 According to the formulation shown in Table 5, in the same manner as in Example 5, a composition for liquid crystal display cell sealing agent (E10) of the present invention was obtained.
The composition for liquid crystal display cell sealant (E10) is composed of an epoxy resin having a weight average of 2.2 epoxy groups in one molecule. %, Inorganic filler content 8%, high softening point polymer fine particle content 1.85%, silane coupling agent content 1.48%, curing agent content 35.73
%, A curing accelerator content of 1.85%, and a solventless type.
The initial viscosity at 25 ° C. measured by an E-type viscometer was 102 Pa ·
s. Liquid crystal display cell sealant composition (E10)
Table 6 shows the physical properties of the sealant relating to. The liquid crystal display cell sealing agent composition (E10) 100 parts, particle diameter 5μ
First, a composition obtained by blending 3 parts of a gap control agent of spherical silica having a particle size of m and mixing sufficiently was applied to an ITO substrate first.
A screen consisting of a total of 4 cells (1 inch in cell size) is printed by screen on each substrate, and each has a width of about 0.5 mm and a sealant applied thickness of about 20 to 22 μm.
Was obtained. Then, after heat treatment for 15 minutes in a 95 ° C. hot air dryer, another ITO substrate to be paired is placed, and after positioning, a press pressure of 0.05 MPa / c is applied.
After a temporary bonding by a rigid single-wafer press heating method at m ² , 170 ° C./5 minutes, a bonding seal test in which a full-curing was performed in a 150 ° C. heating oven for 80 minutes was repeated 10 times. As a result, there was no seal failure due to the generation of bubbles penetrating the seal, and a desired liquid crystal display cell substrate could be manufactured in all lots. Then, after each cell is cut individually,
A cell wedge peeling test and a cell wedge peeling test after a pressure cooker test at 120 ° C. for 3 hours were conducted. Further, the presence or absence of defective seal penetration of the obtained cells and the linearity of the seal line were observed with a magnifying glass. Table 6 shows the results.
It was shown to. Table 6 also shows the results of the sealing function durability test performed using the obtained cells.

Example 11 According to the formulation shown in Table 5, in the same manner as in Example 5, a liquid crystal display cell sealant composition (E11) was obtained.
The composition for liquid crystal display cell sealant (E11) is composed of an epoxy resin having a weight average of 2.8 epoxy groups in one molecule, a content of 27.84%, and a content of rubber-like polymer fine particles of 9. 66%, mineral filler content16.
6%, solvent content 14%, silane coupling agent content 1.9%, curing agent content 25%, curing accelerator content 5%
Consists of Liquid crystal display cell sealant composition (E11)
Table 6 shows the physical properties of the sealant relating to. 5 μm thickness based on 100 parts of the composition for liquid crystal display cell sealant (E11)
First, a composition obtained by blending 5 parts of a gap control agent for short glass fibers and thoroughly mixing the resulting mixture is first treated with a transparent electrode and a polyethylene terephthalate plastic substrate for a liquid crystal cell treated with an alignment film (hereinafter simply referred to as an ITO plastic substrate). ), A pattern consisting of a total of 4 cells (1 inch in cell size) for each of the top, bottom, left, and right per substrate is screen-printed, and the width of the sealant is about 2 mm.
An ITO plastic substrate of 0 to 22 μm was obtained. Then, after heat treatment at 85 ° C. for 20 minutes, another ITO plastic substrate to be paired is placed, and after alignment, it is fully cured by a multi-stage hot press heating method at a press pressure of 0.02 MPa / cm ² and 120 ° C./120 minutes. The joint seal test was repeated 10 times. As a result, there was no seal failure due to the generation of bubbles penetrating the seal, and a desired liquid crystal display cell substrate could be manufactured in all lots.

Also, the composition for a liquid crystal display cell sealing agent (E
11) A composition obtained by mixing 3 parts of a spherical silica gap control agent having a particle diameter of 5 μm with 100 parts and thoroughly mixing the resulting mixture was first placed on an ITO substrate, and each of the four cells (upper, lower, left, and right) per substrate (4 cells in total) A pattern having a cell size of 1 inch) was screen-printed to obtain an ITO substrate having a width of about 0.5 mm and a sealant applied thickness of about 20 to 22 μm. Then, after heat treatment for 15 minutes in a 95 ° C. hot air drier, another ITO substrate to be paired is placed, and after alignment, a rigid single-wafer press heating method is performed at a pressing pressure of 0.05 MPa / cm ² and 170 ° C./5 minutes. After the temporary bonding, the joint seal test was further performed in a heating oven at 150 ° C for 80 minutes.
Repeated times. As a result, there was no seal failure due to the generation of bubbles penetrating the seal, and a desired liquid crystal display cell substrate could be manufactured in all lots. Then
After cutting each cell individually, wedge peel test of the cell,
The cell was subjected to a wedge peeling test after the pressure cooker at 120 ° C., and the presence or absence of defective seal penetration and the linearity of the seal line of the obtained cell were observed with a magnifying glass. The results are shown in Table 6. Table 6 also shows the results of the sealing function durability test performed using the obtained cells.

Example 12 The procedure was the same as in Example 11, except that 25 parts of the curing agent FPI5127 (PPF resin) in Example 11 was replaced with 10 parts of Marcarin S-1 and 15 parts of Marcarin CBA. Thus, a liquid crystal display cell sealing composition (E12) was prepared. Table 6 shows the physical properties of the sealant relating to the composition for a liquid crystal display cell sealant (E12). 100 parts of the composition for liquid crystal display cell sealant (E12) was mixed with 5 parts of a gap control agent of 5 μm thick short glass fiber,
The composition obtained by sufficiently mixing is first screen-printed on an ITO substrate with a pattern comprising a total of 4 cells (1 inch in cell size) for each of the upper, lower, left, and right sides of the substrate, and a width of about 0.1 mm.
An ITO substrate having a thickness of 5 mm and a coating thickness of the sealant of about 20 to 22 μm was obtained. After that, 2 hours at 80 ° C hot air dryer.
After the treatment for 0 minute, another ITO substrate to be paired is placed, and after alignment, a press pressure of 0.03 MPa / cm ² , 180
After performing temporary bonding by a rigid single-wafer hot press method at 150 ° C for 5 minutes, a full-curing bonding test at 150 ° C for 80 minutes was conducted.
Repeated 0 times. As a result, no defective seal or disturbance of the seal line was generated at all due to the generation of bubbles penetrating the seal. In addition, the results of the sealing function durability test performed using the obtained cells were good even after 1000 hours as shown in Table 6.

Example 13 In Example (11), the curing agent FPI5127 (PPF
5 parts OP resin and MILEX SP instead of 25 parts
A liquid crystal display cell sealant composition (E13) was prepared in exactly the same manner as in Example 11 except that the resin was changed to 15 parts.
Table 6 shows the physical properties of the sealant related to the liquid crystal display cell sealant composition (E13). 100 parts of the composition for liquid crystal display cell sealant (E13) was mixed with 5 parts of a gap control agent of short glass fiber having a thickness of 5 μm, and the resulting mixture was thoroughly mixed. A screen consisting of a total of 4 cells (1 inch in cell size), one for each of the top, bottom, left and right, is screen-printed, and is about 0.5 mm in width and about 20 to 22 μm in thickness for applying a sealant.
A substrate was obtained. Then, after another 20 minutes of treatment in a hot air dryer at 80 ° C., another ITO substrate to be paired is placed, and after alignment, a rigid single-wafer hot press method is performed at a pressing pressure of 0.03 MPa / cm ² and 180 ° C./5 minutes. After temporary bonding with
The bonding seal test of hardening at 50 ° C./80 minutes was repeated 10 times. As a result, no defective seal or disturbance of the seal line was generated at all due to the generation of bubbles penetrating the seal. Table 6 shows the results of the joint seal test and the seal function durability test.

[0322]

[Table 5]

[0323]

[Table 6]

Comparative Example 1 An unpurified ortho-cresol novolac epoxy resin having a number average molecular weight of about 890 as measured by GPC, which is a solid epoxy resin and has an ion concentration of 6.2 mS / m (62 μs / cm) in extraction water ( In a solution obtained by dissolving 30 parts of crude novolak epoxy in Table 7 with 20 parts of methyl carbitol, a content of hydrolyzable chlorine of 350 parts was further added.
106 parts by weight of liquid bisphenol A type epoxy resin "Epomic R140 Special Grade" (hereinafter simply referred to as Crude R-140 in Table 7), adipic dihydrazide as a latent epoxy curing agent insoluble in epoxy resin at room temperature (Abbreviated as ADH in Table 7) 18
Part, N-cyanoethyl-2-ethyl- as a curing accelerator
0.2 parts of 4-methylimidazole, titanium oxide "CR-
EL ”5 parts, spherical silica“ SO-E1-6 ”3 parts, Showa Denko Amorphous Alumina UA-5105 14.8 parts,
2 parts of epoxysilane are added, premixed, and then kneaded with a three-roll mill until the solid raw material becomes 5 μm or less, and the kneaded material is subjected to vacuum defoaming treatment. F1) was obtained. The composition for a liquid crystal display cell sealant (F1) is composed of an epoxy resin having a weight average of 2.5 epoxy groups in one molecule, and its content is 68%.
And inorganic filler 11.9%, silane coupling agent 1
%, Latent epoxy curing agent 9%, curing accelerator 0.1%,
Consists of 10% solvent. The initial viscosity at 25 ° C. measured by an E-type viscometer was 29 Pa · s, and the thixotropic index represented by the ratio of one rotation / 10 rotations was 1.7. Table 8 shows the physical properties of the sealant relating to the composition for a liquid crystal display cell sealant (F1).

Composition for Liquid Crystal Display Cell Sealant (F1) 1
5 parts of a glass short fiber gap control agent having a thickness of 5 μm was added to 00 parts, and the composition obtained by mixing well was first placed on an ITO substrate. A pattern having a cell size of 1 inch) was screen-printed to obtain an ITO substrate having a width of about 0.5 mm and a sealant applied thickness of about 20 to 22 μm.
Then, after another 20 minutes of treatment in a hot air dryer at 80 ° C., another ITO glass substrate to be paired is placed, and after alignment, 10 sets of the set are pressed with a multi-stage press at a pressing pressure of 0.03.
The resulting cell was left in an oven at 150 ° C. for 90 minutes while holding it under pressure at MPa / cm ² , and was finally cured and bonded. The results of the seal function durability test performed using the above are shown in the seal durability evaluation column of Table 8. This liquid crystal display cell sealant composition (F1) was found to have good suitability for production of a liquid crystal display element to be heated and bonded by a multi-stage press method.

The composition for a liquid crystal display cell sealant (F
1) 5 parts of a glass short fiber gap control agent having a thickness of 5 μm was blended with 100 parts, and a composition obtained by mixing well was firstly placed on an ITO substrate. A pattern composed of cells (cell size of 1 inch) was screen-printed to obtain an ITO glass substrate having a width of about 0.5 mm and a coating thickness of a sealant of about 20 to 22 μm. Then, the four cells were heated at 80 ° C. for
After the minute treatment, another ITO substrate to be paired is placed, and after positioning, a press pressure of 0.03 MPa / cm ² and 180 ° C.
When the sheet was temporarily bonded by heating with a rigid single-wafer hot press for 4 minutes, generation of bubbles penetrating the seal and failure of the seal line were observed. Therefore, it was found that the composition (F1) for a liquid crystal display cell sealing agent lacked the sheet heat press suitability. Also 2 remaining
The cell is treated with a hot air drier at 80 ° C. for 20 minutes, and another ITO substrate to be paired is placed thereon.
/ Cm ² and then heated at 2 ° C per minute to 130
After the temperature reached ° C., the mixture was further left at the same temperature for 90 minutes to prepare a liquid crystal display cell. Table 8 shows the wedge opening test results and the non-bleeding test results of the cells obtained here.

Comparative Example 2 An unpurified orthocresol novolac type epoxy resin having a number average molecular weight of about 890 as measured by GPC, which is a solid epoxy resin and has an ion concentration of 6.2 mS / m (62 μs / cm) in extraction water ( 25 parts of Epoxy R-367 and 25 parts of Crude Novolak Epoxy in Table 7)
Of a liquid bisphenol F-type epoxy resin EPICLON EP830 having a hydrolyzable chlorine content of 500 ppm, and beforehand dodecanediacid dihydrazide (in the table). 12 D), 1 part of tris (dimethylaminomethylphenol) hydrochloride (DMP-30 hydrochloride in Table 7), 1 part of aminosilane, 2 parts of amorphous silica "MU-120" as an accelerator C as amorphous alumina
Add 10 parts of R-10 and 13 parts of CR-125, pre-mix, then knead with 3 rolls until the solid raw material becomes 5 μm or less, vacuum-deaerate the kneaded material and set forth in Table 7. Of a liquid crystal display cell sealant (F2). The composition for a liquid crystal display cell sealant (F2) is an epoxy resin 45
%, Inorganic filler 25%, silane coupling agent 1%,
Latent epoxy curing agent 12%, curing accelerator 2%, solvent 1
Consists of 5%. The 25 ° C. initial viscosity measured by an E-type viscometer was 35 Pa · s, and the thixotropic index represented by the ratio of 1 rotation / 10 rotation viscosity was 1.6. Table 8 shows the physical properties of the liquid crystal display cell sealing composition (F2).

Liquid Crystal Display Cell Sealant Composition (F2) 1
A composition obtained by mixing 3 parts of a gap control agent of a short glass fiber having a thickness of 5 μm with respect to 00 parts, and thoroughly mixing the resulting mixture was first placed on an ITO substrate for a total of 6 cells (up, down, left and right, per substrate) ( A pattern having a cell size of 1 inch) was screen-printed to obtain an ITO glass substrate having a width of about 0.5 mm and a coating thickness of a sealant of about 20 to 22 μm. After that, the four cells are treated in an 80 ° C. hot air drier for 20 minutes, another ITO substrate to be paired is placed thereon, and after alignment, the heating is performed for 10 minutes by a vacuum-980 hPa and a 180 ° C. vacuum single-wafer hot press. At the time of adhesion, generation of bubbles penetrating the seal and failure of the seal line were observed. Therefore, it was found that the composition (F1) for a liquid crystal display cell sealing agent lacked vacuum single-wafer heat press suitability. The remaining two cells were treated with a hot air dryer at 80 ° C. for 20 minutes, and another ITO substrate to be paired was placed thereon.
After fixing by pressure bonding at a pressure of / cm ² , the temperature was raised from room temperature at 2 ° C./minute to 150 ° C., and then left at the same temperature for 90 minutes to prepare a liquid crystal display cell. Table 8 also shows the observation results of the liquid crystal display function of the obtained cells. In addition, the result of the sealing function durability test performed using the obtained cell showed that display unevenness was remarkable within 250 hours, and the display function deteriorated.

[0329]

[Table 7]

[0330]

[Table 8]

Example 14 68.1 parts of a resin solution obtained by dissolving 43.1 parts of epomic VG3101L in 25 parts of propylene glycol monomethyl ether acetate, 111.2 parts of an NA resin (naphthol aralkyl resin) and DCN (dicyclopentadiene) 372.4 parts of a curing agent solution obtained by previously dissolving 111.2 parts of modified phenol novolak resin) in 150 parts of propylene glycol monomethyl ether acetate,
250 parts of a silicone rubber-containing epoxy resin composition (b),
21.6 parts of 5302T which is a curing accelerator, and CatZ-
4.3, 8.6 parts of KBM403, 12.9 parts of MU-120 as amorphous silica, spherical alumina SO obtained by grafting a silane coupling agent in advance.
-A805 and 262.1 parts of A805 were preliminarily mixed in a batch Dalton mixer, and then kneaded with three rolls until the solid material became 5 μm or less, and further, 100 parts of the kneaded material was mixed with a 6 μm short glass fiber gap control agent. Two parts were added, mixed, and subjected to vacuum defoaming treatment to obtain a composition for liquid crystal display cell sealant (E14) shown in Table 9. The liquid crystal display cell sealant composition (E14) excluding the gap control agent had an epoxy resin content of 21.81% and a solvent content of 17.5.
%, Content of rubber-like polymer fine particles 7.5%, content of inorganic filler 27.5%, content of curing agent 22.24%, content of curing accelerator 2.59%, content of silane coupling agent 0. 86%. Table 10 shows the sealant properties of the liquid crystal display cell sealant composition (E14).

Liquid Crystal Display Cell Sealant Composition (E14)
, A joint seal test was carried out in the same manner as in Example 1, and the results of the joint seal test and the seal durability test were shown in Table 1.
0. The obtained cell was found to have complete cohesive failure of the adhesive and excellent adhesion reliability in both the cell wedge opening test and the same test after pressure cooker. In addition, seal function durability test 10
The display function after 00 hours was good.

Example 15 According to the formulation shown in Table 9, a composition (E15) for a liquid crystal display cell sealing agent of the present invention was obtained in the same manner as in Example 14. The composition for liquid crystal display cell sealant (E15) excluding the gap control agent had an epoxy resin content of 21.
15%, solvent content 16%, rubbery polymer fine particle content 9.85%, inorganic filler content 23.5%, curing agent content 26.5%, curing accelerator content 1%, silane coupling Agent content of 2%. Table 10 shows the physical properties of the sealant composition (E15) for liquid crystal display cell sealants. Using the composition for liquid crystal display cell sealant (E15),
A joint seal test was performed in the same manner as in Example 5, and the results of the joint seal test and the seal durability test are shown in Table 10. The obtained cell was found to be a complete cohesive failure of the adhesive in a wedge opening test of the cell, and was excellent in adhesion reliability. In addition, the display function following display after 1000 hours of the sealing function durability test was good.

Example 16 According to the formulation shown in Table 9, in the same manner as in Example 14, a composition (E16) for a liquid crystal display cell sealant of the present invention was obtained. The liquid crystal display cell sealant composition (E16) excluding the gap control agent had an epoxy resin content of 35.
15%, content of rubber-like polymer fine particles 9.85%, content of inorganic filler 21.3%, content of curing agent 29%, content of curing accelerator 3.2%, content of silane coupling agent 1. 5%. Table 10 shows the sealant properties of the liquid crystal display cell sealant composition (E16). Using the composition for liquid crystal display cell sealing agent (E16), a bonding seal test was carried out in the same manner as in Example 5, and the results of the bonding seal test and the seal durability test are shown in Table 10. The obtained cell was found to be a complete cohesive failure of the adhesive in a wedge opening test of the cell, and was excellent in adhesion reliability. The display function after 1000 hours of the sealing function durability test was good.

Example 17 According to the formulation shown in Table 9, in the same manner as in Example 14, a liquid crystal display cell sealant composition (E17) was obtained. The liquid crystal display cell sealant composition (E17) excluding the gap control agent had an epoxy resin content of 35.
15%, content of rubbery polymer fine particles 9.85%, content of inorganic filler 21.3%, content of curing agent 29%, content of curing accelerator 3.2%, content of silane coupling agent 1.5 %. Table 10 shows the sealant properties of the liquid crystal display cell sealant composition (E17). Using the composition for a liquid crystal display cell sealing agent (E17), a bonding seal test was conducted in the same manner as in Example 5, and the results of the bonding seal test and the seal durability test are shown in Table 10. The obtained cell was found to be a complete cohesive failure of the adhesive in a wedge opening test of the cell, and was excellent in adhesion reliability. The display function after 1000 hours of the sealing function durability test was good.

Example 18 According to the formulation shown in Table 9, a composition (E18) for a liquid crystal display cell sealing agent of the present invention was obtained in the same manner as in Example 14. The liquid crystal display cell sealant composition (E18) excluding the gap control agent had an epoxy resin content of 35.
15%, rubbery polymer fine particle content 9.85%, inorganic filler content 21.3%, hardener content 25.5%,
It consists of a curing accelerator content of 3.2%, a silane coupling agent content of 1.5%, and a high softening point polymer fine particle content of 3.5%. Table 10 shows the physical properties of the sealant composition (E18) for liquid crystal display cell sealants. A bonding seal test was performed in the same manner as in Example 5 using the composition for liquid crystal display cell sealing agent (E18). Table 10 shows the results of the bonding seal test and the results of the seal durability test. The resulting cell is a complete cohesive failure of the adhesive in the cell's wedge opening test,
It was found that the bonding reliability was excellent. The display function after 1000 hours of the sealing function durability test was good.

Example 19 According to the formulation shown in Table 9, a composition (E19) for a liquid crystal display cell sealing agent of the present invention was obtained in the same manner as in Example 14. The composition for liquid crystal display cell sealant (E19) excluding the gap control agent had an epoxy resin content of 34.
57%, solvent content 19.2%, rubbery polymer fine particle content 7.13%, inorganic filler content 17%, hardener content 19%, hardening accelerator content 2.1%, silane coupling Agent content of 1%. Table 10 shows the sealant properties of the liquid crystal display cell sealant composition (E19). Using the composition for liquid crystal display cell sealant (E19),
A joining seal test was performed in the same manner as in Example 5, and the results of the joining seal test and the results of the seal durability test are shown in Table 10. The obtained cell was found to be a complete cohesive failure of the adhesive in a wedge opening test of the cell, and was excellent in adhesion reliability. The display function after 1000 hours of the sealing function durability test was good.

Example 20 According to the formulation shown in Table 9, a composition (E20) for a liquid crystal display cell sealing agent of the present invention was obtained in the same manner as in Example 14. The composition for liquid crystal display cell sealant (E20) excluding the gap control agent had an epoxy resin content of 28.
54%, solvent content 13.2%, rubber-like polymer fine particle content 8.26%, inorganic filler content 17.3%, hardener content 28%, hardening accelerator content 3.2%, silane Coupling agent content of 1.5%. Table 10 shows the physical properties of the sealant composition (E20) for the liquid crystal display cell sealant.
It was shown to. Using the composition for a liquid crystal display cell sealing agent (E20), a bonding seal test was conducted in the same manner as in Example 5, and the results of the bonding seal test and the seal durability test were shown in Table 10.
It was shown to. The obtained cell was found to be a complete cohesive failure of the adhesive in a wedge opening test of the cell, and was excellent in adhesion reliability. In addition, seal function durability test 10
The display function after 00 hours was good.

[0339]

[Table 9]

[0340]

[Table 10]

Comparative Example 3 According to the formulation shown in Table 11, in the same manner as in Comparative Example 1, a composition for a liquid crystal display cell sealant (F3) was obtained. The F3 composition is an example containing no curing accelerator, and the results of measuring the physical properties of the sealant other than the water absorption, TMA measurement (Tg, coefficient of linear expansion), moisture permeability, and surface hardness characteristics are shown in Table 12, and are shown in Table 12. ℃ 9
The coating film obtained by heat curing for 0 minutes is 80 to 150
Only an uncured cured film exhibiting strong adhesiveness in the temperature range of ° C was formed, and showed a property of easily swelling in an acetone solvent. Therefore, it can be said that the F3 composition containing no curing accelerator is a composition having extremely slow thermosetting properties, and the water absorption property evaluation and the TMA
The measurement could not be performed substantially, and the water absorption, Tg, moisture permeability and water absorption in Table 12 could not be measured. Further, 2 parts of a 6 μm short glass fiber gap control agent was mixed with 100 parts of the F3 composition, and subjected to a bonding seal test in the same manner as in Example 1. As a result, bleeding and the formation of bubbles through the seal were hardly observed, but a bonded cell was formed. Than was done,
The sheet heat press suitability was judged to be unsuitable. Also,
As shown in Table 12, the results of the seal durability test using the obtained cells were such that the liquid crystal display function lacked durability.

Comparative Example 4 According to the formulation shown in Table 11, in the same manner as in Example 1, a composition for a liquid crystal display cell sealant (F4) was obtained. The F4 composition is an example using an imidazole monomer as a curing accelerator. The sealing agent properties of the liquid crystal display cell sealing agent composition (F4) are shown in Table 12, but it was apparent that the F4 composition had a fatal problem in pot life at room temperature and lacked coating workability. . The F4 composition 100 immediately after production
The mixture was mixed with 2 parts of a gap control agent of 6 μm short glass fiber and subjected to a bonding seal test in the same manner as in Example 1. As a result, the composition after pre-drying was hard and had no wettability to the substrate. The cell obtained in the joint seal test
It was found that half of them were not substantially adhered and were sealants lacking in sheet heat press suitability. Table 12 shows the observation results of the obtained cells. Room temperature 23 ° C for 10 hours after production
When the bonding seal test was performed using the F4 composition left as described above in the same manner as in Example 1, all the pieces exhibited poor adhesion,
The sealant was found to be remarkably lacking in sheet heat press suitability. Table 12 shows the results of a seal durability test performed on a cell manufactured and subjected to the above-described joint seal test using the F4 sealant immediately after the manufacture, and having a certain degree of adhesion. As a result, the durability was found to be almost good, but lack of storage stability is fatal.

Comparative Example 5 According to the formulation shown in Table 11, a composition (F5) for a liquid crystal display cell sealant was obtained in the same manner as in Example 1. The F5 composition is an example using triphenylphosphine as a curing accelerator. Table 12 shows the physical properties of the sealant composition (F5) for a liquid crystal display cell sealant, but the F5 composition clearly has a serious problem in pot life at room temperature and lacks coating workability. 10 of the F5 composition immediately after production
0 parts were mixed with 2 parts of a gap control agent of 6 μm short glass fiber, and subjected to a bonding seal test in the same manner as in Example 1. As a result, the composition after pre-drying was hard and poor in wettability to a substrate. Substantially half of the cells obtained in the joint seal test had substantial adhesion defects, and were found to be sealants lacking in sheet heat press suitability. Table 12 shows the observation results of the obtained cells. Using the F5 composition left at room temperature and 25 ° C. for 12 hours after production, when a bonding seal trial was conducted in the same manner as in Example 1, poor adhesion or defective adhesion was observed in all of them, and leakage or peeling phenomenon occurred during liquid crystal injection. It was found that the sealant was remarkably lacking in sheet heat press suitability. Table 12 shows the results of a seal durability test performed on the cells manufactured and subjected to the above-described joint seal test using the F5 sealant immediately after the manufacture, and where adhesion was observed.
It was shown to. As a result, the durability was found to be almost good,
Lack of storage stability is fatal.

Comparative Example 6 According to the formulation shown in Table 11, in the same manner as in Example 1, a liquid crystal display cell sealant composition (F6) was obtained. In the F6 composition, the blending amount of the polyhydric phenol curing agent was 9.9% by mass, and the curing agent equivalent ratio to the epoxy resin was too small (epoxy group:
(Equivalent ratio of active phenolic hydroxyl group is 1: 0.3). Table 12 shows the physical properties of the liquid crystal display cell sealing compound composition (F6). Apparently, the sealant was found to have a fatal problem of producing only a cured product lacking heat resistance rigidity. The sealant coating film obtained when cured by heat at 150 ° C. for 90 minutes forms only an uncured cured film exhibiting strong adhesiveness in the range of 80 to 150 ° C. and has a property of easily swelling in an acetone solvent. Was. Therefore, there is a problem in that the F6 sealant composition to which the amount of the curing agent added is too small gives only a cured product which is fragile at room temperature and lacks strong heat-resistant rigidity. Since a smooth film-like cured product having no tack was not obtained, the evaluation of moisture permeability and water absorption properties could not be substantially performed.
The water absorption and the moisture permeability in 2 were not measurable. 2 parts of a 6 μm short glass fiber gap control agent was mixed with 100 parts of the F6 composition, and subjected to a bonding seal test in the same manner as in Example 1. As a result, no bleeding was observed, but the generation of bubbles penetrating the seal was observed with a probability of 25%. Since a bonded cell having the same shape was obtained, the suitability for single-wafer heat press was judged to be almost suitable. Further, the obtained cell was subjected to a wedge opening test and a seal durability test, and the results are shown in Table 12, but the result lacks the liquid crystal display function durability.

Comparative Example 7 According to the formulation shown in Table 11, in the same manner as in Example 1, a composition for a liquid crystal display cell sealing agent (F7) was obtained. In the F7 composition, the blending amount of the polyhydric phenol curing agent was 52% by mass, and the curing agent equivalent ratio to the epoxy resin was too large (1: 4 as the equivalent ratio of the epoxy group to the active phenolic hydroxyl group when converted to the equivalent). This is an example. Table 12 shows the physical properties of the liquid crystal display cell sealant composition (F7). The sealant has a fatal problem of producing only a hardened material which is fragile when bent by about 10 °. Therefore, each test of surface hardness, TMA (Tg, coefficient of linear expansion), moisture permeability, and water absorption was substantially impossible, and in Table 12, it was expressed as unmeasurable. 2 parts of a 6 μm short glass fiber gap control agent was mixed with 100 parts of the F7 composition, and subjected to a bonding seal test in the same manner as in Example 1. As a result, no bleeding was observed, but the occurrence of seal-penetrating bubbles was observed with a probability of more than half, and the adhesive was brittle and easily collapsed when handling the cells, so that only one normal cell was obtained. Did not. Therefore, the sheet heat press suitability was determined to be inappropriate. Since the seal durability test was practically impossible, the results of the seal durability test in Table 12 indicated that the cells could not be manufactured.

Comparative Example 8 According to the formulation shown in Table 11, in the same manner as in Example 1, a composition for a liquid crystal display cell sealant (F8) was obtained. The F8 composition is a composition comprising an epoxy resin, an esterified polyhydric phenol resin curing agent, a silane coupling agent, an inorganic filler, and a high boiling point solvent. As with the F3 composition of Example 3, F8
It is evident that the composition has a significant lack of thermosetting properties, and furthermore a significant lack of cell suitability. Especially 150 ° C
The sealant coating film obtained after heat curing for 90 minutes was substantially in an uncured state, formed only a brittle and fragile cured film, and showed a property of easily dissolving and swelling in an acetone solvent. As a result, the most important problem is that the sealant (F8) composition lacks thermosetting properties.

Liquid Crystal Display Cell Sealant Composition (F8) 1
For the 00 parts, the gap of 5 μm thick short glass fiber was used.
A composition obtained by mixing 5 parts of a control agent and thoroughly mixing
First, on the ITO substrate, 1 inch size per substrate
Screens a pattern consisting of a total of four cells, one each for the top, bottom, left and right
About 0.5mm wide and about 20-22μm thick
An ITO substrate was obtained. Then, 120 ° C hot air dryer
After processing for 30 minutes, place another ITO substrate to be paired,
After alignment, press pressure 0.03MPa / cm ^Two, 2
Temporarily bonded by rigid single-wafer press heating at 50 ° C for 4 minutes
After that, put it in a heating oven at 200 ° C for 5 hours.
Repeatedly performed the bonding seal test for final curing adhesion 10 times
Was. As a result, defective seals due to the generation of bubbles penetrating the seal
And disturbance of the seal line were observed with a probability of 60%. Yo
Therefore, it was found that the sheet heat pressability was poor. Ma
Also, we went in a cell where the sealing property was managed somehow
Seal durability test results are not as good as Table 12
Was.

Comparative Example 9 According to the formulation shown in Table 11, a composition (F9) for a liquid crystal display cell sealant of a comparative example was obtained in the same manner as in Example 1. F
No. 9 composition comprises a phosphazene compound (PZO) as a curing accelerator and an imidazole epoxy adduct (PN
-23) in a total amount of 16% by mass. As is clear from the properties of the sealant shown in Table 12, the cured product has low water absorbency and low moisture permeability, but has a problem in adhesive seal reliability because it is hard and brittle. 2 parts of a 6 μm short glass fiber gap control agent was mixed with 100 parts of the F9 composition, and subjected to a bonding seal test in the same manner as in Example 1. As a result, many gap failures and seal defects were observed, and it was found that cell suitability was lacking. Therefore, the result display regarding the seal durability in Table 12 indicates that the cell cannot be manufactured.

[0349]

[Table 11]

[0350]

[Table 12]

Example 21 According to the formulation shown in Table 13, a composition (E21) for a liquid crystal display cell sealing agent of the present invention was obtained in the same manner as in Example 1. The liquid crystal display cell sealant composition (E21) excluding the gap control agent had an epoxy resin content of 29.
44%, solvent content 13.2%, rubbery polymer fine particle content 8.26%, inorganic filler content 18%, hardener content 27.8%, hardening accelerator content 2%, silane cup The content of the ring agent is 1.3%. Table 14 shows the physical properties of the liquid crystal display cell sealing compound composition (E21). Using the composition for liquid crystal display cell sealing agent (E21), a bonding seal test was carried out in the same manner as in Example 1, and the results of the bonding seal test and the seal durability test are shown in Table 14. In the obtained cell, a partial cohesive failure of the adhesive was observed in a wedge opening test of the cell, and it was found that the adhesion reliability was good. In addition, seal function durability test 100
The display function after 0 hour was good.

Example 22 According to the formulation shown in Table 13, in the same manner as in Example 1, a liquid crystal display cell sealing compound composition (E22) was obtained. The composition for liquid crystal display cell sealant (E22) excluding the gap control agent had an epoxy resin content of 21.
1%, content of rubber-like polymer fine particles 6.9%, content of inorganic filler 25.5%, content of curing agent 24.5%, content of curing accelerator 1.5%, content of silane coupling agent 2
% And a solvent content of 18.5%. Table 14 shows the physical properties of the sealant composition (E22) for liquid crystal display cell sealants. Using the composition for a liquid crystal display cell sealing agent (E22), a bonding seal test was performed in the same manner as in Example 1. Table 14 shows the results of the bonding seal test and the seal durability test. The obtained cell was found to be a complete cohesive failure of the adhesive in a wedge opening test of the cell, and was excellent in adhesion reliability. In addition, seal function durability test 100
The display function after 0 hour was good.

Example 23 According to the formulation shown in Table 13, in the same manner as in Example 1, a liquid crystal display cell sealant composition (E23) was obtained. The composition for liquid crystal display cell sealant (E23) excluding the gap control agent had an epoxy resin content of 22.2.
5%, rubber-like polymer fine particle content 7.5%, inorganic filler content 24.5%, curing agent content 23%, curing accelerator content 2%, silane coupling agent content 2.5%,
The solvent content was 18%. Table 14 shows the physical properties of the liquid crystal display cell sealing compound composition (E23). Using the composition for a liquid crystal display cell sealing agent (E23), a bonding seal test was performed in the same manner as in Example 1, and the results of the bonding seal test and the seal durability test are shown in Table 14. In the obtained cell, a partial cohesive failure of the adhesive was observed in a wedge opening test of the cell, and it was found that the adhesion reliability was good. The display function after 1000 hours of the sealing function durability test was good.

Example 24 According to the formulation shown in Table 13, in the same manner as in Example 1, a liquid crystal display cell sealant composition (E24) was obtained. The composition for liquid crystal display cell sealant (E24) excluding the gap control agent had an epoxy resin content of 22.2.
5%, rubber-like polymer fine particle content 7.5%, inorganic filler content 24.5%, curing agent content 23%, curing accelerator content 2%, silane coupling agent content 2.5%,
The solvent content was 18%. Table 14 shows the physical properties of the sealant composition (E24) for liquid crystal display cell sealants. Using the composition for a liquid crystal display cell sealing agent (E24), a bonding seal test was carried out in the same manner as in Example 1. Table 14 shows the results of the bonding seal test and the seal durability test. The obtained cells were partially cohesive failure of the adhesive in the cell wedge opening test, and it was found that the adhesion reliability was good. The display function after 1000 hours of the sealing function durability test was good.

Example 25 According to the formulation shown in Table 13, a composition (E25) for a liquid crystal display cell sealing agent of the present invention was obtained in the same manner as in Example 1. The composition for liquid crystal display cell sealant (E25) excluding the gap control agent had an epoxy resin content of 22.2.
5%, rubber-like polymer fine particle content 7.5%, inorganic filler content 24.5%, curing agent content 23%, curing accelerator content 2%, silane coupling agent content 2.5%,
The solvent content was 18%. Table 14 shows the physical properties of the sealant composition (E25) for liquid crystal display cell sealants. Using the composition for liquid crystal display cell sealing agent (E25), a bonding seal test was conducted in the same manner as in Example 1. Table 14 shows the results of the bonding seal test and the seal durability test. In the obtained cell, a partial cohesive failure of the adhesive was observed in a wedge opening test of the cell, and it was found that the adhesion reliability was good. The display function after 1000 hours of the sealing function durability test was good.

Example 26 According to the formulation shown in Table 13, in the same manner as in Example 1, a liquid crystal display cell sealant composition (E26) of the present invention was obtained. The composition for liquid crystal display cell sealant (E26) excluding the gap control agent had an epoxy resin content of 37.
2%, content of rubber-like polymer fine particles 7.8%, content of inorganic filler 21.3%, content of curing agent 29%, content of curing accelerator 3.2%, content of silane coupling agent 1.5
%. Composition for liquid crystal display cell sealant (E2
Table 14 shows the physical properties of the sealant of 6). Using the composition for a liquid crystal display cell sealing agent (E26), a bonding seal test was performed in the same manner as in Example 1, and the results of the bonding seal test and the seal durability test are shown in Table 14. The obtained cell was partially cohesive failure of the adhesive in a wedge opening test of the cell, and it was found that the cell had excellent adhesion reliability. The display function after 1000 hours of the sealing function durability test was good.

Example 27 To 100 parts of the composition for liquid crystal display cell sealant (E5) of the present invention prepared in Example 5, conductive beads (trade name: Micropearl AU-205) manufactured by Sekisui Fine Chemical Co., Ltd.
A composition (E27) was obtained by adding 5.28 parts. Table 14 shows the physical properties of the sealant composition (E27) for liquid crystal display cell sealants. Composition for liquid crystal display cell sealant (E2
Using 7), a joint seal test was performed in the same manner as in Example 1. Table 14 shows the joint seal test results and the seal durability test results. The obtained cell was partially cohesive failure of the adhesive in a wedge opening test of the cell, and it was found that the cell had excellent adhesion reliability. The display function after 1000 hours of the sealing function durability test was good. Table 14 also shows the measurement results related to the anisotropic conductivity.
It was found that both anisotropic conductivity and seal adhesion suitability were excellent.

Example 28 100 parts of the composition for liquid crystal display cell sealant (E12) of the present invention prepared in Example 12 was mixed with conductive beads (trade name: Micropearl AU-20, manufactured by Sekisui Fine Chemical Co., Ltd.).
5 "(7.52 parts) to give a composition (E28).
Table 14 shows the physical properties of the sealant composition (E28) for liquid crystal display cell sealants. Using the composition for a liquid crystal display cell sealing agent (E28), a bonding seal test was carried out in the same manner as in Example 1. Table 14 shows the results of the bonding seal test and the seal durability test. The obtained cell was partially cohesive failure of the adhesive in a wedge opening test of the cell, and it was found that the cell had excellent adhesion reliability. The display function after 1000 hours of the sealing function durability test was good. The measurement results relating to the anisotropic conductivity are also shown in Table 14, and it was found that both the anisotropic conductivity and the suitability for sealing adhesion were excellent.

[0359]

[Table 13]

[0360]

[Table 14]

[0361]

As is clear from Examples 1 to 28, the composition for a liquid crystal display cell sealant of the present invention has a water absorption of 2% or less as measured by immersing the cured product in boiling water for 30 minutes. It is clear that it has low characteristics. Also, a. Good storage stability and coating workability; High temporary adhesion after pre-cure; c. Compatible with the single-wafer press heat bonding method, and is excellent in non-bleeding property, non-penetrating foam property, linearity of seal line, and precise gap width controllability. E. Excellent in adhesive seal reliability. The cured product is excellent in low moisture permeability at 80 ° C. The presence of electrically conductive ions migrating from the composition is kept low; Adhesive durability at high temperatures and long-term display stability of the obtained liquid crystal display cell in a high-temperature and high-humidity environment can be ensured.

In particular, it is clear that the liquid crystal display device produced with the composition for a liquid crystal display cell sealant of the present invention has a high sealing function durability of more than 1,000 hours. On the other hand, as is apparent from Comparative Example 1 or Comparative Example 2,
A liquid crystal display cell sealant composition containing a large amount of free ions lacks display function durability, and at the same time, an epoxy resin composition containing dihydrazide as a main curing agent has a high water absorption exceeding 2%. And Comparative Example 3
This is an example in which the curing accelerator of the present invention is not contained as a composition component for a liquid crystal display cell sealant of the present invention, but only an uncured or brittle cured product can be obtained. Comparative Example 4
Is an example using 2-ethyl-4-methylimidazole well known as a curing accelerator, but the sealant has no pot life aptitude and has a fatal problem in coating workability. Further, Comparative Example 5 is an example using triphenylphosphine, which is well known as a curing accelerator. However, similarly to Comparative Example 4, the pot life is extremely short, and it is apparent that there is a fatal problem in coating workability. It became.

Comparative Examples 6 and 7 are examples in which the amount of the curing agent is too small or too large. In either case, poor curing or poor adhesion is exhibited, which is substantially unsuitable for liquid crystal display cell production. Is evident. In Comparative Examples 8 and 9, there is no or excessive hardening accelerator, but the former has poor curing and lacks adhesiveness, and the latter has a hard and brittle hardened body, and furthermore has a gap controllability. It is clear that the adhesiveness and adhesiveness are remarkably lacking. That is, the liquid crystal display element using the liquid crystal display cell sealant of the present invention or the liquid crystal display element manufactured using the liquid crystal display cell sealant composition can ensure long-term display stability in a high-temperature and high-humidity environment. Is the feature. The liquid crystal display element of the present invention can be used as a display used in a high-temperature and high-humidity situation such as a vehicle.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02F 1/1339 505 G02F 1/1339 505 1/1341 1/1341 F-term (Reference) 2H089 LA24 MA03Y NA22 NA38 NA40 NA42 NA44 NA45 QA06 QA07 RA05 RA10 RA13 RA14 4J002 BG04Y CC02X CC04X CC07X CD00W CE00X DA067 DA077 DC007 EJ016 EJ076 FA08Y FD01Y FD117 FD14X GJ02 4J036 AA01 DB05 DB09 DC25 DD07 FB05 FB07 FB08 FB07 FB08 FB08

Claims (21)

[Claims] 1. A seal for a liquid crystal display element comprising a cured product of a composition for a liquid crystal display cell sealant, wherein the cured product has a water absorption of 2% by mass or less. Agent. 2. A film having a thickness of 80 μm passing through a cured film having a thickness of 100 μm.
^{2. The} sealant for a liquid crystal display cell according to claim 1, wherein the sealant has a moisture permeability at 200 ° C. of 200 g / m ² · 24 hrs or less. 3. The specific resistance of the liquid crystal after contacting at 145 ° C. for 1 hour at a ratio of 1 part by mass of the liquid crystal to 0.1 part by mass of the sealant is 250 times the specific resistance of the liquid crystal before contact. 3. The sealant for a liquid crystal display cell according to claim 1, wherein the ratio is not more than twice. 4. An epoxy resin comprising a polyhydric phenol compound,
4. The sealant for a liquid crystal display cell according to claim 1, wherein the sealant is cured with at least one curing agent selected from a polyhydric phenol resin and an esterified product thereof. 5. The sealant for a liquid crystal display cell according to claim 4, wherein a curing accelerator comprising at least one selected from an alkyl urea derivative and a phosphazene compound is used. 6. A curing agent comprising (1) an epoxy resin and (2) at least one selected from polyhydric phenol compounds, polyhydric phenol resins and their esterified products, and (3)
A composition for a liquid crystal display cell sealing agent, comprising a curing accelerator comprising at least one selected from an alkyl urea derivative and a phosphazene compound. 7. A curing agent comprising (1) 20 to 88.9 parts by mass of an epoxy resin and (2) a curing agent comprising at least one member selected from the group consisting of a polyhydric phenol compound, a polyhydric phenol resin and an ester thereof. 7. The composition for a liquid crystal display cell sealant according to claim 6, comprising (3) 0.1 to 20 parts by mass of a curing accelerator comprising at least one selected from an alkyl urea derivative and a phosphazene compound. 8. The composition for a liquid crystal display cell sealant according to claim 6, wherein the ionic conductivity of an aqueous solution obtained by mixing the composition with pure water of the same mass is 10 mS / m or less. object. 9. The composition for a liquid crystal display cell sealant according to claim 6, wherein a water absorption of a cured product of the composition is 2% by mass or less. 10. The composition for a liquid crystal display cell sealant according to claim 6, wherein a moisture permeability at 80 ° C. passing through a cured film of the composition having a thickness of 100 μm is not more than 200 g / m ² · 24 hrs. 11. The specific resistance of the liquid crystal after contacting at 145 ° C. for 1 hour at a ratio of 1 part by mass of the liquid crystal to 0.1 part by mass of the composition is 250 times the specific resistance of the liquid crystal before the contact. The composition for a liquid crystal display cell sealant according to claim 6 or 7, wherein the ratio is not more than twice. 12. The composition for a liquid crystal display cell sealant contains 1 to 25% by mass of rubber-like polymer fine particles having a softening point temperature of 0 ° C. or less and primary particles having an average particle size of 5 μm or less in the composition for a liquid crystal display cell sealant. The composition for a liquid crystal display cell sealant according to claim 6 or 7, wherein 13. The curing agent is a phenol novolak resin, a phenol aralkyl resin, a naphthol novolak resin, a naphthol aralkyl resin, an alicyclic compound-modified phenol novolak resin, an alicyclic compound-modified naphthol novolak resin, a polycyclic aromatic compound-modified novolak resin, Polyhydric phenol monomer, polyvinylphenol, vinylphenol copolymer, polyisopropenylphenol, polyisopropenylphenol copolymer, esterified phenol novolak resin, esterified phenol aralkyl resin, esterified naphthol novolak resin, esterified naphthol Aralkyl resin, esterified alicyclic compound modified phenol novolak resin, esterified alicyclic compound modified naphthol novolak resin, esterified polycyclic aromatic compound modified novolak The resin is at least one selected from the group consisting of a resin, an esterified polyphenol monomer, an esterified polyvinyl phenol, an esterified vinyl phenol copolymer, an esterified polyisopropenyl phenol, and an esterified polyisopropenyl phenol copolymer.
Or the composition for a liquid crystal display cell sealing agent according to 7. 14. An alkyl urea derivative comprising 3- (p-chlorophenyl) -1,1-dimethylurea, 3- (o, p-dichlorophenyl) -1,1-dimethylurea, 2,4- [bis
(1,1-dimethylurea)] toluene, 2,6- [bis (1,
1-dimethylurea)] at least one selected from toluene
8. The composition for a liquid crystal display cell sealant according to claim 6, wherein the composition is a seed. 15. The phosphazene compound represented by the general formula (1)
2) The composition for a liquid crystal display cell sealant according to claim 6 or 7, wherein the composition is at least one kind represented by the following chemical formula (1). Embedded image (Wherein, R ^a to R ^f are a hydrogen atom, carbon number 1 to 1)
Represents a straight-chain, branched or cyclic alkyl group of 0, or an aryl or aralkyl group having 6 to 10 carbon atoms, all of which may be the same or different. ) 16. A composition for a liquid crystal display cell sealant further comprising 1 to 15 parts by mass of conductive beads with respect to 100 parts by mass of the composition according to claim 6 or 7. 17. A liquid crystal display device using the sealant for a liquid crystal display cell according to claim 1. 18. A liquid crystal display device obtained by using the composition for a liquid crystal display cell sealant according to claim 6. Description: 19. TN liquid crystal, STN liquid crystal, ferroelectric liquid crystal,
17. In the production of a liquid crystal display device using any one of antiferroelectric liquid crystals, the composition for a liquid crystal display cell sealant according to any one of claims 6 to 16 is used for bonding a liquid crystal cell substrate made of glass or plastic. After printing or dispensing the component parts, pre-curing at a temperature of 50 to 120 ° C, aligning and overlaying the other counter substrate, temporarily fixing, and then heat-pressing the counter substrate at 80 to 200 ° C. Then, the substrate is bonded and fixed to a uniform thickness in the range of 1 to 7 μm to form a liquid crystal display cell, a liquid crystal material is injected into the cell, and the injection hole is filled with a photocurable liquid crystal sealant composition or two liquids. A method for producing a liquid crystal display device, characterized in that pores are sealed with a liquid crystal sealant composition. 20. TN liquid crystal, STN liquid crystal, ferroelectric liquid crystal,
17. In the production of a liquid crystal display device using any one of antiferroelectric liquid crystals, the composition for a liquid crystal display cell sealant according to any one of claims 6 to 16 is used for bonding a liquid crystal cell substrate made of glass or plastic. After printing or dispensing on the constituent parts, pre-curing at a temperature of 50 to 120 ° C, dropping liquid crystal and overlaying the other substrate so that air is not trapped, aligning and temporarily fixing, and then temporarily fixing the substrate. Is heat-pressed at 80 to 150 ° C., and the substrate is bonded and fixed to a uniform thickness in the range of 1 to 7 μm.
A method for producing a liquid crystal display element, characterized in that pores are sealed with a liquid type liquid crystal sealant composition. 21. A liquid crystal display device obtained by the method for manufacturing a liquid crystal display device according to claim 19.