JP2016117887A - Curable resin excellent in flexibility after curing, (meth)acryl curable resin and liquid crystal display sealing agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin forming a cured article having flexibility for maintaining an adhesion state without problems even when a flexible liquid crystal display is bent, low in liquid crystal contamination property and hardly affecting liquid crystal orientation and a liquid crystal sealing agent composition containing the curable resin.SOLUTION: There is provided a curable resin represented by the formula (1), where X is each independently H, OH, glycidyloxy or methyl glycidyloxy, Ris each independently H, OH, glycidyl or methylglycidyl, Ris each independently H or methyl, an A ring is each independently an aromatic ring or a hetero aromatic ring having the total of carbon atoms and hetero atoms of 5 or more, Y is alkylene oxide or a hydrocarbon chain having a vinyl group in a side chain or an unsaturated group in a main chain and m is an integer of 1 to 7.SELECTED DRAWING: None

Description

  The present invention relates to a curable resin and (meth) acrylated curable resin suitable for a liquid crystal sealant that exhibit excellent flexibility even after curing, and a liquid crystal sealant composition containing these curable resins. .

  In the manufacture of a liquid crystal display device such as a liquid crystal panel, for example, a liquid crystal sealant is applied to the outer periphery of one of the two substrates constituting the liquid crystal panel, and a predetermined amount of liquid crystal is dropped on one of the substrates. A liquid crystal dropping method is widely used in which two substrates are bonded together under vacuum and then returned to atmospheric pressure to fill the liquid crystal between the substrates and cure the liquid crystal sealant.

  In the liquid crystal dropping method, a radical polymerization reactive compound mainly composed of an epoxy acrylate compound is widely used as a liquid crystal sealant from the viewpoint of rapid curing (see, for example, Patent Document 1).

JP 2007-297470 A

  In the liquid crystal dropping method, a sealing agent is applied to one of the two substrates in a frame shape to form a frame seal, the liquid crystal is dropped onto one of the substrates, the two substrates are bonded together under vacuum, and UV irradiation is performed. Then, after the liquid crystal sealant is photocured, the liquid crystal sealant is thermally cured at a temperature equal to or higher than the NI point (nematic isotropic point) of the liquid crystal, and the liquid crystal sealant is thermally cured and simultaneously aligned.

  In the case of a large panel such as a TV, since the panel is large, there is a certain distance from the liquid crystal dripping point to the frame seal, and the liquid crystal is uncured from when the liquid crystal is dripped and bonded to the panel before UV irradiation. The liquid crystal sealant in the state was not in contact or contact time was short, and the liquid crystal sealant was mainly in contact with the liquid crystal after photocuring.

  On the other hand, in a small liquid crystal panel, which has been in increasing demand due to the spread of smartphones and tablet terminals in recent years, the distance from the liquid crystal dripping point to the frame seal is short, so the liquid crystal sealant must be applied between the pasting and UV irradiation. It is in contact with the liquid crystal in an uncured state or has a long contact time. Therefore, the liquid crystal contamination in the uncured state of the liquid crystal sealant becomes a problem than before.

  Conventional radical polymerization reactive liquid crystal sealing agents mainly composed of an epoxy compound containing an epoxy / acrylic compound cannot be said to sufficiently satisfy the demand for solving such problems.

  In recent years, the market development of a flexible liquid crystal display such as electronic paper that is safe, lightweight, and can be bent freely is expected. The flexible liquid crystal display is manufactured using a flexible substrate such as a plastic film instead of the conventional rigid glass substrate.

  As for the liquid crystal sealant, the conventional one forms a relatively rigid cured product, so it is suitable for bonding substrates such as glass with little shape change, but in flexible displays consisting of flexible substrates such as films. However, in conventional products, breakage or peeling occurs due to a shape change due to bending or contraction of the substrate.

  From such a viewpoint, a liquid crystal sealant having sufficient flexibility even after curing is required as a sealant particularly suitable for a flexible liquid crystal display.

  In view of the above, an object of the present invention is to form a cured product having flexibility that can maintain an adhesive state without problems even when a flexible liquid crystal display is bent, and has low liquid crystal contamination and hardly affects liquid crystal alignment. It is providing the liquid crystal sealing agent composition containing curable resin and the said curable resin.

［式中、ｍは、１〜７の範囲の数であり、Ｒ^１は、それぞれ互いに独立に水素原子、グリシジル基又はメチルグリシジル基であり、Ｒ^２は、それぞれ互いに独立に水素原子又はメチル基であり、Ａ環は、それぞれ互いに独立に炭素原子数、及びヘテロ原子数の合計が５以上であり、且つ１つ以上の芳香環、又はヘテロ芳香環を含む基であり、Ｘは、互いに独立に、水素原子、水酸基、グリシジルオキシ基、又はメチルグリシジルオキシ基であり、Ｙは、下記式（１ａ）：

（式中、Ｙ^１は、それぞれ互いに独立に炭素原子数２〜５のアルキレン基であり、ｎは１〜２５０の範囲の数である）、下記式（１ｂ）：

（式中、Ｙ^２は、それぞれ互いに独立に直接結合又は炭素数１若しくは２のアルキレン基であり、Ｒ^３はそれぞれ互いに独立に水素原子又はメチル基であり、ｐとｑはそれぞれ互いに独立に０以上の数であり、且つそれらの合計は１〜２００の範囲の数である）、又は前記式（１ｂ）中の不飽和結合の一部又は全部を水素化した構造の基であり、前記Ｒ^１及びＸに関して、グリシジル基又はメチルグリシジル基であるＲ^１と、グリシジルオキシ基又はメチルグリシジルオキシ基であるＸの合計の個数の平均ｘは１以上である。］。
（２）前記式（１）において、Ａ環に含まれる炭素原子数が４〜４０であり、酸素原子数が０〜５であり、窒素原子数が０〜５であり、硫黄原子数が０〜５であり、且つＡ環に含まれる環構造の数が１〜５である、（１）に記載の硬化性樹脂。
（３）（１）又は（２）に記載の硬化性樹脂のエポキシ基、水酸基及び不飽和結合の少なくとも一部と（メタ）アクリル酸及び／又は（メタ）アクリル酸無水物とを反応させて得られる（メタ）アクリル化硬化性樹脂。
（４）（１）又は（２）に記載の硬化性樹脂及び／又は（３）に記載の（メタ）アクリル化硬化性樹脂を含む、液晶シール剤組成物。
（５）前記液晶シール剤組成物における、硬化性樹脂及び／又は（メタ）アクリル化硬化性樹脂の含有量が５〜９５重量％である、（４）に記載の液晶シール剤組成物。
（６）前記液晶シール剤組成物が、さらに、エチレン性不飽和基及び／又はエポキシ基を有する化合物Ｈ（但し、前記硬化性樹脂及び（メタ）アクリル化硬化性樹脂を除く）を含む、（４）又は（５）に記載の液晶シール剤組成物。 The present invention includes the following aspects.
(1) Curable resin represented by the following formula (1):

[Wherein, m is a number in the range of 1 to 7, R ¹ is independently a hydrogen atom, glycidyl group or methyl glycidyl group, and R ² is independently a hydrogen atom or methyl group, respectively. A ring is a group having a total of 5 or more carbon atoms and heteroatoms independently of each other and containing one or more aromatic rings or heteroaromatic rings, and X is independent of each other. And a hydrogen atom, a hydroxyl group, a glycidyloxy group, or a methylglycidyloxy group, and Y represents the following formula (1a):

(Wherein Y ¹ are each independently an alkylene group having 2 to 5 carbon atoms, and n is a number in the range of 1 to 250), the following formula (1b):

Wherein Y ² is a direct bond or an alkylene group having 1 or 2 carbon atoms, independently of each other, R ³ is a hydrogen atom or a methyl group, independently of each other, and p and q are each independently 0 And the sum thereof is a number in the range of 1 to 200), or a group having a structure in which a part or all of the unsaturated bonds in the formula (1b) are hydrogenated, and the R Regarding ¹ and X, the average x of the total number of R ¹ which is a glycidyl group or a methyl glycidyl group and X which is a glycidyloxy group or a methyl glycidyloxy group is 1 or more. ].
(2) In the formula (1), the ring A contains 4 to 40 carbon atoms, 0 to 5 oxygen atoms, 0 to 5 nitrogen atoms, and 0 sulfur atoms. The curable resin according to (1), which is ˜5 and the number of ring structures contained in the A ring is 1˜5.
(3) Reacting at least part of the epoxy group, hydroxyl group and unsaturated bond of the curable resin according to (1) or (2) with (meth) acrylic acid and / or (meth) acrylic anhydride. Obtained (meth) acrylated curable resin.
(4) A liquid crystal sealant composition comprising the curable resin according to (1) or (2) and / or the (meth) acrylated curable resin according to (3).
(5) The liquid crystal sealant composition according to (4), wherein the content of the curable resin and / or the (meth) acrylated curable resin in the liquid crystal sealant composition is 5 to 95% by weight.
(6) The liquid crystal sealant composition further comprises a compound H having an ethylenically unsaturated group and / or an epoxy group (however, excluding the curable resin and the (meth) acrylated curable resin). The liquid crystal sealing agent composition as described in 4) or (5).

  According to the present invention, a curable resin that forms a cured product having flexibility that can maintain an adhesive state without problems even when the flexible liquid crystal display is bent, and that has low liquid crystal contamination and does not easily affect liquid crystal orientation, and A liquid crystal sealant composition containing the curable resin is provided.

  Hereinafter, the present invention will be described in detail. In this specification, (meth) acryl means methacryl and / or acryl, and (meth) acrylate means methacrylate and / or acrylate.

[Curable resin of the present invention]
The curable resin of the present invention is represented by the following formula (1).

  The curable resin of the present invention has a flexible part composed of an ether part and a predetermined group Y of a block enclosed in parentheses with a subscript m, and the curable resin of the present invention is cured. The obtained cured product is considered to exhibit flexibility and rubber elasticity in the flexible part, and is excellent in flexibility. As represented by the formula (1), the curable resin of the present invention has a flexible polymer structure, and accordingly, the crosslinking density of the cured product of the curable resin of the present invention may be appropriately reduced. It is thought that it contributes to exhibiting the above flexibility.

  Further, the curable resin of the present invention has an aromatic ring-containing structure called A-ring while having the above-mentioned flexible portion, and the curable resin of the present invention having such a predetermined structure has low liquid crystal contamination.

(About m)
In formula (1), m is a number in the range of 1 to 7, and is preferably a number in the range of 1 to 5 from the viewpoint of the viscosity and handling properties of the curable resin of the present invention. It is more preferable that the number be in the range. The curable resin of the present invention can be produced by, for example, a production method described later, and in that case, may be a mixture of a plurality of types of compounds having different numbers of m.

(About X)
In Formula (1), X is a hydrogen atom, a hydroxyl group, a glycidyloxy group, or a methyl glycidyloxy group each independently. When X is a hydroxyl group, a glycidyloxy group or a methylglycidyloxy group, the portion can cause a crosslinking reaction as described later, and a (meth) acryl group can be introduced into the portion.

  From the viewpoint of low liquid crystal contamination, such X is preferably a hydroxyl group and a glycidyloxy group.

(About R ¹ )
In the above formula (1), R ¹ each independently represents a hydrogen atom, a glycidyl group or a methyl glycidyl group. As will be described later, the group containing R ¹ can cause a crosslinking reaction, and a (meth) acryl group can also be introduced into this portion. When m is a number of 2 or more, R ^{1 in} each block enclosed in parentheses with a subscript m is also independent and may be the same or different from each other. Good.

From the viewpoint of low liquid crystal contamination, such R ¹ is preferably a hydrogen atom or a glycidyl group.

In the curable resin of the present invention represented by the above formula (1), R ¹ which is a glycidyl group or a methyl glycidyl group and X which is a glycidyloxy group or a methyl glycidyloxy group (that is, R ¹ having an epoxy group) The average x of the total number of X) is 1 or more, preferably 2 or more. In this way, the curable resin has a certain number of crosslinkable groups and the above-mentioned flexible portion, so that the cured product has excellent curability and adhesiveness required for the liquid crystal sealant. Flexibility (hereinafter also referred to as “post-curing flexibility”) can also be achieved.

  The x is a liquid crystal sealant composition containing the curable resin of the present invention, which will be described later, for example, workability such as applicability affected by viscosity, and physical properties such as strength after curing affected by crosslink density. From the viewpoint, it is preferably 2 or more as described above, more preferably 2 to 16, and further preferably 2 to 8.

  For x, the average molecular weight and molecular weight distribution of the curable resin are measured by high performance liquid chromatography (HPLC), liquid chromatography mass spectrometry (LC-MS), and gel filtration / permeation chromatography (GPC / GFC). Further, by measuring the epoxy equivalent of the curable resin, x in the above formula (1) can be calculated from the measurement result.

(About R ² )
In the above formula (1), R ² is each independently a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of low liquid crystal contamination of the curable resin of the present invention. In addition, when m is a number of 2 or more, R ^{2 in} each block enclosed in parentheses with a subscript m is also independent and may be the same or different from each other. Good.

(About ring A)
In the above formula (1), the A ring is a group having a total of 5 or more carbon atoms and heteroatoms independently of each other and containing one or more aromatic rings or heteroaromatic rings. The total number of carbon atoms and heteroatoms is 5 or more means that when the entire A ring is viewed, the carbon atoms and heteroatoms constituting the ring, and the groups having carbon atoms and heteroatoms are bonded to the ring constituent atoms. If so, the total number of carbon atoms and heteroatoms including those groups is 5 or more.

  About A ring, from the viewpoint of the viscosity of curable resin of this invention and the liquid-crystal sealing compound composition mentioned later, and handling property, the carbon atom number contained in it is 4-40, and the number of oxygen atoms is 0-5. The number of nitrogen atoms is 0 to 5, the number of sulfur atoms is 0 to 5, and the number of ring structures contained in the A ring is preferably 1 to 5.

  The ring structure (aromatic ring and heteroaromatic ring) contained in the A ring may be a single type or two or more types, and the ring structure may be a monocyclic structure or a condensed ring structure. It may be. A plurality of these ring structures may be bonded to each other through a direct bond or a linking group.

  Examples of this linking group include an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 2 to 4 carbon atoms, an ether group, an ester group, a keto group, a sulfide group, and a sulfonyl group. In the above formula (1), the oxygen atom bonded to the A ring and X and the A ring may be bonded via this linking group.

  Moreover, these ring structures may each independently have a substituent. Examples of such substituents include alkyl groups, alkoxy groups, acyl groups, formyl groups, carboxyl groups, ester groups, cyano groups, nitro groups, sulfo groups, amide groups, hydroxyl groups, mercapto groups, silyl groups, and the like. It is done.

  Examples of the ring structure included in the A ring include benzene ring, naphthalene ring, fluorene ring, anthracene ring, furan ring, pyrrole ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, thiazine ring, and these And those having the above substituents bonded to the ring.

  In addition, when m is a number of 2 or more, the A rings in the individual blocks enclosed in parentheses with the subscript m are also independent and may be the same or different from each other. Good.

(About Y)
Next, in the above formula (1), Y is a group having a structure in which a part or all of unsaturated bonds in the following formula (1a), (1b) or the formula (1b) is hydrogenated. When m is a number of 2 or more, Ys in individual blocks enclosed in parentheses with a subscript m are also independent and may be the same or different from each other. .

In Formula (1a), Y ¹ is each independently an alkylene group having 2 to 5 carbon atoms, and n is a number in the range of 1 to 250. Examples of the alkylene group include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and a neopentyl group. From the viewpoint of the post-curing flexibility of the curable resin of the present invention and the liquid crystal contamination, Y ¹ is preferably an ethylene group or a tetramethylene group, and from the viewpoint of the flexibility and handling properties of the curable resin of the present invention. N is preferably a number in the range of 5 to 70, more preferably a number in the range of 10 to 50.

In addition, when n is a number of 2 or more, Y ^{1 in} each repeating unit enclosed in parentheses with a subscript of n is also independent, and may be the same or different from each other. Also good.

In Formula (1b), Y ² is a direct bond or an alkylene group having 1 or 2 carbon atoms, each independently of each other, R ³ is a hydrogen atom or a methyl group, each independently of each other, and p and q are It is independently a number of 0 or more, and the sum thereof is a number in the range of 1 to 200. When p or q is 2 or more, there are a plurality of repeating units enclosed in parentheses with these subscripts, but R ^{3 in} each of these repeating units is also independent and identical to each other. Or different. Further, these repeating units may be bonded at random within the range of p and q described above.

  The total number of p and q is preferably a number in the range of 5 to 70, more preferably a number in the range of 10 to 50, from the viewpoints of handling properties and post-curing flexibility of the curable resin of the present invention. is there.

(About m, n, p, q)
M, which represents the number of predetermined blocks (repeating units) relating to the formula (1) described above, is the charged amount of the synthetic raw material of the curable resin of the present invention described later, the resin (or (meth) acrylated described later) It can be estimated from the GPC measurement result of the curable resin. The total value of n, p, and q can be estimated from the GPC measurement result of the curable resin (or (meth) acrylated curable resin described later), and these are GPC measurement of the synthetic raw material of the curable resin. It can also be estimated from the results. Further, the values of p and q can be analyzed by IR or the like.

<Characteristics of curable resin>
The viscosity of the curable resin of the present invention described above is usually 1,000 to 2,000,000 mPa · s. As will be described later, the curable resin of the present invention is suitable for use in liquid crystal sealants, but when used in such applications, the viscosity of the curable resin is preferably from the viewpoint of securing an appropriate viscosity for the liquid crystal sealant. Is 3000 to 2,000,000 mPa · s. In the present specification, the viscosity is a value measured at 25 ° C. using an E-type viscometer.

The viscosity of the curable resin can be adjusted, for example, by changing m in the formula (1) and / or changing the abundance ratio of a hydroxyl group (for example, when R ¹ is a hydrogen atom) in the curable resin.

Moreover, when using curable resin for a liquid-crystal sealing compound, from the viewpoint of making adhesiveness and a softness | flexibility compatible, the epoxy equivalent becomes like this. Preferably it is 400-10000 g / eq, More preferably, it is 500-5000 g / eq. . The epoxy equivalent of the curable resin is the average molecular weight of the curable resin and the epoxy group (for example, glycidyl group) per block (repeating unit) enclosed in parentheses with the subscript m in the above formula (1). It can be adjusted by the number of R ¹ ).

  Furthermore, the curable resin of the present invention has a small NI point change. The NI point is a temperature at which the liquid crystal undergoes a phase transition from a nematic phase to an isotropic phase (isotropic phase) (the phase transition temperature can be measured from an endothermic peak top using a differential thermal analyzer). The NI point of the liquid crystal is determined by the mixed composition of each component of the liquid crystal and is a unique value for each formulation. When a raw material or sealant with high liquid crystal contamination is mixed with liquid crystal, the NI point changes greatly. Conversely, when the raw material or sealant has low liquid crystal contamination, the change of the NI point is small.

  Specifically, the NI point change of the curable resin of the present invention is usually in the range of −5 ° C. to + 5 ° C., preferably in the range of −3 ° C. to + 3 ° C. The details of the NI point change measurement method will be described in the examples described later.

[(Meth) acrylated curable resin]
The curable resin of the present invention can be made into a (meth) acrylated curable resin by reacting (meth) acrylic acid and / or (meth) acrylic anhydride. The olefin part of the (meth) acrylic group can cause a crosslinking reaction, and even in the (meth) acrylated curable resin, it achieves excellent flexibility while ensuring the adhesiveness required for the liquid crystal sealant. Can do.

More specifically, the introduction of the (meth) acrylic group into the curable resin of the present invention is carried out by using an epoxy group (for example, when R ¹ is a glycidyl group), a hydroxyl group, and an unsaturated bond (for example, Y is selected) of the curable resin. Occurs for at least a portion of the group of formula (1b). In addition, when an epoxy group is opened by addition of a (meth) acryl group or the like, a hydroxyl group is generated. However, a (meth) acryl group may be further introduced into the hydroxyl group.

  The introduction of the (meth) acryl group is caused by reacting the curable resin of the present invention with a (meth) acrylic acid-based compound such as acrylic acid, methacrylic acid, or an anhydride, ester compound, or acid halide thereof. Can be done by.

<Characteristics of (meth) acrylated curable resin>
Like the curable resin of the present invention, the (meth) acrylated curable resin of the present invention exhibits preferable characteristics for use in a liquid crystal sealant.

  That is, the viscosity of the (meth) acrylated curable resin of the present invention is usually 1,000 to 2,000,000 mPa · s, and preferably 3,000 to 2,000,000 mPa · s from the viewpoint of securing an appropriate viscosity for the liquid crystal sealant.

  Further, the (meth) acrylated curable resin of the present invention has a small NI point change, and the NI point change is usually in the range of -5 ° C to + 5 ° C, preferably in the range of -3 ° C to + 3 ° C.

[Method for producing curable resin]
Next, the manufacturing method of curable resin of this invention is demonstrated.
The method for producing the curable resin includes a step of reacting the compound E represented by the following formula (2) or (3) with the compound F represented by the following formula (4).

In the formulas (2) and (3), Y ¹ , n, Y ² , R ³ , p and q are as defined above, and R ⁴ is independently a hydrogen atom, a glycidyl group or methyl glycidyl. It is a group. Furthermore, in the formula (3), a part or all of the unsaturated bonds in the repeating unit enclosed in parentheses with a subscript p or q may be hydrogenated.

In Formula (4), the X and A rings are as defined above, and R ⁵ is a hydrogen atom, a glycidyl group, or a methyl glycidyl group.

For example, when —OR ⁴ present at the molecular end of Compound E is a glycidyloxy group or a methyl glycidyloxy group, at least one of —OR ⁵ or X in Compound F is a hydroxyl group, and these glycidyl group or methyl Compound F is linked to the end of Compound E by a ring-opening reaction between the glycidyl group and the hydroxyl group. And if necessary, a free hydroxyl group in the obtained compound (a synthetic intermediate G described later, which is a curable resin of the present invention when it has one or more epoxy groups in the molecule) M is 1 in formula (1) by adjusting at least a part of (for example, a hydroxyl group newly generated by a ring-opening reaction) to glycidyl ether as described later so that x is 1 or more. In this case, the curable resin of the present invention is obtained.

In Compound F, when —OR ⁵ and X are groups capable of opening an epoxy group such as a hydroxyl group, both of —OR ⁵ and X react with the glycidyloxy group or methylglycidyloxy group of Compound E. can do. In the compound thus obtained, the curable resin of the present invention in which m in the formula (1) is 2 or more can be obtained by glycidyl etherification of a free hydroxyl group as described below, if necessary. In addition, m can be adjusted with the preparation amount of the compounds E and F. Even when -OR ⁵ and X are both groups capable of opening an epoxy group, m is 1 by adjusting the preparation amount. The curable resin of the invention can be obtained.

  In addition, compound E and F may be used individually by 1 type, respectively, or may be used in combination of 2 or more type.

  The molecular weight of the compound E represented by the formula (2) or (3) is preferably 500 to 10,000. In addition, in this specification, molecular weight is the number average molecular weight of standard polystyrene conversion measured by GPC.

Compounds E and F are commercially available or can be easily prepared from commercially available compounds according to known methods. For example, as the compound E of the formula (2) in which R ⁴ is a hydrogen atom and Y ¹ is an ethylene group, those having various numbers of repeating units (n) as polyethylene glycol are available, and the desired range of What is necessary is just to select the compound which has n suitably. Moreover, n can also be estimated from the GPC measurement result of polyethylene glycol.

In addition, polyethylene glycol introduces a glycidyl group or the like at the end of polyethylene glycol by reacting with a compound capable of introducing a glycidyl group or a methylglycidyl group such as epichlorohydrin (hereinafter also referred to as “epoxidized compound”). This means that R ⁴ can be easily converted from a hydrogen atom to a glycidyl group or the like. This also applies to the other examples of compounds E and F described below wherein R ⁴ or R ⁵ is a hydrogen atom.

Further, as the compound E of the formula (2) in which R ⁴ is a hydrogen atom and Y ¹ is a propylene group, those having various repeating unit numbers (n) are available as polypropylene ether glycol. For example, EXCENOL420, EXCENOL720, EXCENOL1020, EXCENOL2020 (above, manufactured by Asahi Glass Co., Ltd.) and the like can be mentioned.

In addition, the compound E of the formula (2) in which R ⁴ is a hydrogen atom and Y ¹ is a trimethylene group can be prepared, for example, according to the method described in JP 2013-515144 A, with various repeating unit numbers (n ) Can be produced as polytrimethylene ether glycol.

Further, as the compound E of the formula (2) in which R ⁴ is a hydrogen atom and Y ¹ is a tetramethylene group, those having various repeating unit numbers (n) are available as polytetramethylene ether glycol. For example, PTMG650, PTMG850, PTMG1000, PTMG1300, PTMG1500, PTMG1800, PTMG2000 (above, manufactured by Mitsubishi Chemical Corporation) and the like can be mentioned.

Further, as the compound E of the formula (3) in which R ³ is a hydrogen atom and R ⁴ is a hydrogen atom, compounds having various repeating unit numbers (p, q) are available as terminal hydroxyl group-introduced polybutadiene. For example, NISSO PB G-1000, G-2000 (above, manufactured by Nippon Soda Co., Ltd.), Poly bd R-45HT (produced by Idemitsu Kosan Co., Ltd.) and the like can be mentioned.

Further, R ³ is a hydrogen atom, R ⁴ is a hydrogen atom, and a part or all of unsaturated bonds in a repeating unit enclosed in parentheses with a p or q suffix are hydrogenated As the compound E of (3), compounds having various numbers of repeating units (p, q) are available as hydrides of terminal hydroxyl group-introduced polybutadiene. For example, NISSO-PB GI-1000, GI-2000 (above, Nippon Soda Co., Ltd.) etc. can be mentioned.

Further, as compound E of the formula (3) in which R ³ is a methyl group and R ⁴ is a hydrogen atom, compounds having various repeating unit numbers (p, q) are available as terminal hydroxyl group-introduced polyisoprene. . For example, Poly ip (made by Idemitsu Kosan Co., Ltd.) etc. can be mentioned.

A compound in which R ³ is a methyl group, R ⁴ is a hydrogen atom, and a part or all of unsaturated bonds in a repeating unit enclosed in parentheses with a p or q suffix are hydrogenated. As the compound E of (3), compounds having various numbers of repeating units (p, q) are available as hydrides of terminal hydroxyl group-introduced polyisoprene. For example, EPOL (made by Idemitsu Kosan Co., Ltd.) can be mentioned.

Further, as compound F in which R ⁵ is a hydrogen atom, X is a hydroxyl group, and the A ring satisfies the specified number of atoms and ring structure, resorcinol, 2- (4-hydroxyphenyl) ethanol, bisphenol A, bisphenol M, bisphenol P, 1,6-naphthalenediol, 2-ethyl-9,10-anthracenediol, 3,4-thiophenediol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and the like. .

Moreover, as the compound F in which R ⁵ is a hydrogen atom, X is a hydrogen atom, and the A ring satisfies the specified number of atoms and ring structure, phenol, 4-α-cumylphenol, 4-methoxyphenol, 4-hydroxyquinoline etc. are mentioned.

R ⁵ in R ⁴ and Compound F in the compound E, respectively, from the viewpoint of curing after flexibility and low liquid stain resistance of the cured resin obtained are either the hydrogen atom of R ⁴ and R ^5, other glycidyl It is preferably a group.

  Compound E and Compound F are obtained, for example, by reacting Compound E and Compound F in the presence of an alkali so as to produce the curable resin of the present invention, and then, if necessary, the obtained synthetic intermediate G is reacted with a suitable epoxidized compound in the presence of a suitable catalyst. In the above-described reaction, the charging amount is adjusted so that m in the curable resin is a number in the range of 1 to 7, preferably 1 to 5, and more preferably 1 to 3. The said compound may be used individually by 1 type, or may be used in combination of 2 or more type.

  About the number of m, in the case of the below-mentioned Example, when synthesizing the synthetic intermediate G, it can control as follows. For example, in Synthesis Example 1, the equivalent ratio of the epoxy group and bisphenol A (corresponding to compound F) in compound E-1 is 1.0: 2.5. If 1.0: 1.5, the number of m increases. Conversely, even when 1.0: 10, 1.0: 100, 1.0: 1000, or the like, it does not become less than 1.

From the viewpoint of reactivity, it is preferable that one of R ⁴ in Compound E and R ⁵ in Compound F is a hydrogen atom, and the other is a glycidyl group or a methyl glycidyl group.

  Examples of the alkali include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, tetramethylammonium chloride, Quaternary ammonium salts such as methyltrioctylammonium chloride, methyltridecylammonium chloride and benzyltrimethylammonium chloride are preferred, and sodium hydroxide or quaternary ammonium salts are more preferred. These alkalis are preferably used as an aqueous solution, but in some cases, a powder or solid alkali can be added simultaneously with water or separately. Moreover, these alkalis may be used individually by 1 type, or may be used in combination of 2 or more type.

The amount of alkali used is such that when R ⁴ is a hydrogen atom and R ⁵ is a glycidyl group from the viewpoint of the rapid progress of the reaction and the cost of synthesis, the alkali may be equal to or more than the equivalent of the hydroxyl group, and R ⁴ is glycidyl. Group or a methyl glycidyl group, and when R ⁵ is a hydrogen atom, a catalytic amount may be sufficient, which is 0.0001 to 0.1 equivalent of the hydroxyl group of Compound F.

  The amount of the epoxidized compound is preferably 0.05 to 20 equivalents, more preferably 0.05 to 15 equivalents, based on the hydroxyl group contained in the raw material compound. The amount used is adjusted by the average number x of epoxy groups in the target curable resin, but x exceeds the average number of hydroxyl groups in the raw material compound even if a large excess amount is used relative to the hydroxyl group. There is no.

  Catalysts include tertiary amines such as trimethylamine, trioctylamine and tridecylamine, tetramethylammonium chloride, methyltrioctylammonium chloride, methyltridecylammonium chloride and benzyl chloride from the viewpoint of reaction time, cost, and reaction activity. A quaternary ammonium salt such as trimethylammonium is preferred, and a quaternary ammonium salt is more preferred. These may be used alone or in combination of two or more.

  The amount of the catalyst used is preferably 0.0001 to 0.5 equivalent, more preferably 0.01 to the hydroxyl group contained in the raw material compound from the viewpoint of appropriately securing the reaction rate while suppressing side reactions. 0.1 equivalent.

  The reaction with the alkali is preferably performed at 50 to 250 ° C., more preferably 70 to 200 ° C., further preferably 100 to 170 ° C., and the reaction with the epoxidized compound is preferably 25 to 100 ° C. More preferably, it is performed at 30 to 80 ° C, and further preferably at 40 to 60 ° C. In the reaction, a solvent inert to the reaction such as hydrocarbon, ether or ketone can be used, but when an epoxidized compound is used in excess, the compound also functions as a solvent. Not required.

  Purification of the curable resin after completion of the reaction can be performed by a conventional method. For example, excess epoxidized compound is distilled off, and a water-insoluble solvent such as hydrocarbon is added as necessary, followed by washing with water. The target curable resin of the present invention can be obtained by removing the generated salt and catalyst.

From the viewpoint that general-purpose raw materials can be used as the compound E and the compound F, the production method of the curable resin of the present invention is the compound E1 in which R ⁴ in the compound E is a glycidyl group (diglycidyl etherified compound of the compound E; for example, polyethylene Glycol diglycidyl ether) and R ⁵ in compound F is a compound F1 (for example, bisphenol A), the compound E1 and the compound F1 are reacted to react the compound E1 with the compound F1. Step 1 to obtain a synthetic intermediate G of step 1 and Step 2 to epoxidize the hydroxyl group of the synthetic intermediate G to obtain a curable resin in which part or all of the hydroxyl groups of the synthetic intermediate G are epoxidized. Is preferred.

<Method for producing (meth) acrylated curable resin>
Furthermore, (meth) acrylic group is introduced into at least a part of the epoxy group, hydroxyl group and unsaturated bond through the step 3 of reacting the curable resin with a (meth) acrylic acid compound in the presence of a basic catalyst. In addition, the (meth) acrylated curable resin of the present invention can be obtained.

  As a basic catalyst, the well-known basic catalyst used for reaction with an epoxy resin and (meth) acrylic acid can be used. A polymer-supported basic catalyst in which a basic catalyst is supported on a polymer can also be used. As the basic catalyst, a trivalent organic phosphorus compound, a salt thereof, an amine compound and a salt thereof are preferable. These basic catalysts may be used individually by 1 type, or may be used in combination of 2 or more type. In addition, the basic atom of a basic catalyst is phosphorus and / or nitrogen.

  Examples of the trivalent organic phosphorus compound include alkylphosphines and salts thereof such as triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine, triphenylphosphine, tri-m-tolylphosphine, tris (2, Arylphosphines such as 6-dimethoxyphenyl) phosphine and salts thereof, phosphorous acid triesters such as triphenylphosphite, triethylphosphite and tris (nonylphenyl) phosphite and salts thereof. Of these, triphenylphosphine is preferable.

  Trivalent phosphine / ethyl bromide, triphenyl phosphine / butyl bromide, triphenyl phosphine / octyl bromide, triphenyl phosphine / decyl bromide, triphenyl phosphine / isobutyl bromide, triphenyl phosphine / Examples thereof include propyl chloride, triphenylphosphine / pentyl chloride, triphenylphosphine / hexyl bromide and the like.

  Examples of the amine compound include secondary amines such as diethanolamine, tertiary amines such as triethanolamine, dimethylbenzylamine, trisdimethylaminomethylphenol, trisdiethylaminomethylphenol, 1,5,7-triazabicyclo [4. 4.0] dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene (Me-TBD), 1,8-diazabicyclo [ 5.4.0] Undec-7-ene (DBU), 6-dibutylamino-1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] Examples include strongly basic amines such as non-5-ene (DBN) and 1,1,3,3-tetramethylguanidine. Among these, 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) is preferable.

  Examples of the salt of the amine compound include benzyltrimethylammonium chloride, benzyltriethylammonium chloride, and a salt of the above strongly basic amine.

  The polymer for supporting the basic catalyst is not particularly limited, and a polymer obtained by crosslinking polystyrene with divinylbenzene, a polymer obtained by crosslinking acrylic resin with divinylbenzene, or the like is used. These polymers are solvents (for example, methyl ethyl ketone, methyl isobutyl ketone, toluene, etc.) and raw materials used for the reaction between the curable resin obtained by the production method including step 1 or steps 1 and 2, and a (meth) acrylic acid compound. Insoluble in the product. Moreover, these polymers may be used individually by 1 type, or may be used in combination of 2 or more type.

  A polymer-supported basic catalyst is obtained by chemically bonding a basic catalyst to an insoluble polymer or introducing a basic catalyst into a monomer, polymerizing the monomer, and then three-dimensionally crosslinking with a crosslinking monomer such as divinylbenzene. Such a cross-linking results in a polymer-supported basic catalyst that is insoluble in solvents such as methyl ethyl ketone, methyl isobutyl ketone, and toluene.

  Specific examples of the polymer-supported basic catalyst include diphenylphosphinopolystyrene, 1,5,7-triazabicyclo [4.4.0] dec-5-enepolystyrene, N, N- (diisopropyl) aminomethylpolystyrene. N- (methylpolystyrene) -4- (methylamino) pyridine and the like. These polymer-supported basic catalysts may be used singly or in combination of two or more.

As the polymer-supported basic catalyst, a commercially available one may be used. Examples of commercially available polymer-supported basic catalysts include PS-PPh ₃ (diphenylphosphinopolystyrene, manufactured by Biotage), PS-TBD (1,5,7-triazabicyclo [4.4.0] deca-5. -Enpolystyrene, manufactured by Biotage Corp.) and the like.

  In the method for producing a (meth) acrylated curable resin of the present invention, the temperature in the reaction step between the curable resin obtained by the production method including step 1 or steps 1 and 2 and the (meth) acrylic acid compound is preferably 60-120 degreeC, More preferably, it is 80-120 degreeC, More preferably, it is 90-110 degreeC.

  In the presence of a catalyst, when the curable resin obtained by the production method including step 1 or steps 1 and 2 is reacted with a (meth) acrylic acid compound, in the reaction system and on the reaction system in order to prevent gelation. It is necessary to maintain an appropriate oxygen concentration in the gas phase. For example, when air is actively blown into the reaction system, it is necessary to be careful because it may cause oxidation of the catalyst and cause a decrease in activity.

  Regarding the reaction between the curable resin obtained by the production method including step 1 or steps 1 and 2, and the (meth) acrylic acid-based compound, the (meth) acrylated curable resin obtained by this reaction is active energy such as ultraviolet rays. It is desirable to carry out the reaction in a container that shields from ultraviolet rays because it is cured by radiation. In addition, the reaction between the curable resin obtained by the production method including Step 1 or Steps 1 and 2 and the (meth) acrylic acid compound is a good solvent for the curable resin in order to prevent gas phase polymerization. However, in this case, it is necessary to remove the solvent after completion of the reaction. For this reason, it is preferable to perform the said reaction without a solvent. Examples of the reflux solvent include acetone, methyl ethyl ketone, toluene and the like.

[Liquid crystal sealant composition]
The curable resin and (meth) acrylated curable resin of the present invention (hereinafter collectively referred to as “the curable resin of the present invention”) have the various characteristics described above, and are used as liquid crystal sealants. It has a preferred viscosity for use, low liquid crystal stain and excellent post-cure flexibility.

  Therefore, the liquid crystal sealant composition using the curable resin of the present invention is excellent in handling properties and hardly affects the orientation of the liquid crystal even when it contacts the liquid crystal in an uncured state by the liquid crystal dropping method. Therefore, it is difficult to disturb the orientation of the liquid crystal, and when used in a flexible device such as a flexible liquid crystal display, even if the flexible substrate sandwiching the cured liquid crystal sealant is bent, its excellent flexibility and stress relaxation Due to the effect, cracking of the liquid crystal seal portion, peeling from the substrate, and the like hardly occur.

  Specifically, the viscosity of the liquid crystal sealing agent composition of the present invention is usually 1,000 to 2,000,000 mPa · s, preferably 10,000 to 1,000,000 mPa · s. Further, the viscosity of the liquid crystal sealing agent composition can be adjusted by the structure of the curable resin of the present invention, components that can be included in the liquid crystal sealing agent composition described below, and the addition of a solvent.

Such a liquid crystal sealant composition of the present invention containing the curable resin of the present invention has a storage elastic modulus of a cured liquid crystal sealant obtained by curing it, usually from room temperature (25 ° C.). ) in a ^{1.0 × 10 3 ~3.0 × 10 9} Pa, preferably ^{1.0 × 10 3 ~1.0 × 10 9} Pa. In addition, the measuring method of a storage elastic modulus is demonstrated in detail at the term of the below-mentioned Example.

  In addition, the glass transition temperature (Tg) of the cured liquid crystal sealant obtained by curing the liquid crystal sealant composition of the present invention is usually 80 ° C. or lower, preferably 40 ° C. or lower, more preferably, from the viewpoint of flexibility. Is 30 ° C. or lower, more preferably room temperature (25 ° C.) or lower, and particularly preferably −80 to 25 ° C.

  The liquid crystal sealant composition of the present invention includes the curable resin of the present invention, and the content of the curable resin and the like in the liquid crystal sealant composition is usually 5 to 95% by weight, and is flexible and adhesive. From the viewpoint of the influence on the liquid crystal orientation, the content is preferably 10 to 95% by weight.

  Moreover, the liquid-crystal sealing compound composition of this invention may further contain the various components demonstrated below in the range which does not impair the effect of this invention according to the various characteristics calculated | required by the said use.

<Compound H>
The liquid crystal sealant composition of the present invention may contain a curable component in addition to the curable resin of the present invention, for example, a conventional ethylenically unsaturated group and / or used as a main component of a liquid crystal sealant. The liquid crystal sealant composition containing the curable resin of the present invention together with the compound H having an epoxy group (for example, an oligomer in which a part of the epoxy group of the bisphenol A type epoxy resin is (meth) acrylated) is compound H only Compared with the case, the flexibility of the cured liquid crystal sealant is greatly improved.

  Examples of the compound H having an ethylenically unsaturated group include (meth) acrylate compounds, aliphatic acrylamide compounds, alicyclic acrylamide compounds, acrylamide compounds containing aromatics, and N-substituted acrylamide compounds.

  Examples of the (meth) acrylate compound include paracumylphenoxyethylene glycol (meth) acrylate, t-butyl (meth) acrylate, ethoxylated phenyl (meth) acrylate, benzyl (meth) acrylate, and glycidyl (meth) acrylate. Aliphatic (meth) acrylates and aromatic ring-containing (meth) acrylates can be mentioned.

  Moreover, as the compound H which has an ethylenically unsaturated group, a monofunctional, bifunctional, trifunctional, or polyfunctional radically polymerizable unsaturated compound is also mentioned.

  Examples of the monofunctional radically polymerizable unsaturated compound include hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate from the viewpoint of ensuring the viscosity and flexibility of the liquid crystal sealant composition. , Isooctyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclohexyloxyethyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl Oxyethyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate, tert-butyl (meth) acrylate and diethylene glycol monoethyl ether (meth) acrylate 1 or more compounds selected from the group consisting of benzoate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and cyclohexyl One or more compounds selected from the group consisting of (meth) acrylates are more preferred.

  Examples of the bifunctional radically polymerizable unsaturated compound include tricyclodecane dimethanol di (meth) acrylate, dimethylol dicyclopentane di (meth), from the viewpoint of ensuring the viscosity and flexibility of the liquid crystal sealant composition. Acrylate, EO-modified 1,6-hexanediol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, polyester di (meth) acrylate (for example, ARONIX M-6100, Selected from the group consisting of polyethylene glycol di (meth) acrylate (for example, 4G, manufactured by Shin-Nakamura Chemical Co., Ltd.), and silicon di (meth) acrylate (for example, EBECRYL 350, manufactured by Daicel Ornex) Preferably one or more compounds More preferred are dimethylol dicyclopentane di (meth) acrylate and / or EO or PO-modified bisphenol A di (meth) acrylate. Among them, (meth) acrylate having a bisphenol A skeleton without a hydroxyl group is preferable, and as such (meth) acrylate, Kyoeisha Chemical Co., Ltd., Light acrylate BP-4EAL (EO adduct diacrylate of bisphenol A), BP-4PA (PO adduct diacrylate of bisphenol A) and the like are commercially available.

  Examples of the trifunctional or polyfunctional radically polymerizable unsaturated compound include EO-modified glycerol tri (meth) acrylate (trifunctional), PO-modified glycerol from the viewpoint of ensuring the viscosity and flexibility of the liquid crystal sealant composition. From the group consisting of tri (meth) acrylate (trifunctional), pentaerythritol tri (meth) acrylate (trifunctional), dipentaerythritol hexa (meth) acrylate (hexafunctional) and pentaerythritol tetra (meth) acrylate (tetrafunctional) One or more selected compounds are preferable, and EO-modified glycerol tri (meth) acrylate is more preferable.

  Next, the compound H having an epoxy group is preferably a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol AD type epoxy compound, a phenol novolac type epoxy compound, a cresol novolak type epoxy compound, a naphthalene type epoxy compound, It is at least one compound selected from the group consisting of resorcinol type epoxy compounds, these hydrogenated compounds and alicyclic epoxy compounds, more preferably bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, naphthalene type epoxy compounds. And at least one compound selected from the group consisting of resorcinol type epoxy compounds, more preferably bisphenol A type epoxy compounds.

Specific examples of the bisphenol A type epoxy compound include EPICLON 850S, 860, 1055, and EXA-850 CRP manufactured by DIC.
Specific examples of the hydrogenated bisphenol A type epoxy compound include KRM-2408 manufactured by ADEKA and YX-8034 manufactured by JER.
Specific examples of the bisphenol F type epoxy compound include EPICLON 830S manufactured by DIC.
Specific examples of naphthalene type epoxy compounds include EPICLON HP-4032D and HP-7200H manufactured by DIC.
Specific examples of the phenol novolac type epoxy compound include EPICLON N-740 and N-770 manufactured by DIC.
Specific examples of the cresol novolac type epoxy compound include EPICLON N-660 and N-670 manufactured by DIC.
Specific examples of the resorcinol type epoxy compound include Denacol EX-201 manufactured by Nagase ChemteX Corporation.
Specific examples of the alicyclic epoxy compound include 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (Celoxide 2021P manufactured by Daicel), 1,2: 8,9-diepoxy limonene. (Celoxide 3000 manufactured by Daicel), 1,2-epoxy-4-vinylcyclohexane (Celoxide 2000 manufactured by Daicel), 1,2-epoxy-4- (2 of 2,2-bis (hydroxymethyl) -1-butanol -Oxiranyl) cyclohexane adduct (EHPE3150 manufactured by Daicel).

  Examples of the compound H having an ethylenically unsaturated group and an epoxy group include partial (meth) acrylate-modified epoxy compounds obtained by reacting an epoxy group-containing compound with a (meth) acrylic acid compound. A partial (meth) acrylated epoxy compound obtained by reacting an A-type epoxy resin with (meth) acrylic acid is preferred.

  The partial (meth) acrylated epoxy compound obtained by reacting the bisphenol A type epoxy resin with (meth) acrylic acid is obtained, for example, as follows.

  First, bisphenol A type epoxy resin and (meth) acrylic acid are reacted in the presence of a basic catalyst, preferably a trivalent organic phosphoric acid compound and / or an amine compound. At this time, the reaction ratio is 10 to 90 equivalent% of (meth) acrylic acid with respect to 1 equivalent of epoxy group. Next, the reaction product is purified by removing the basic catalyst by filtration, centrifugation, and / or washing with water. As said basic catalyst, the well-known basic catalyst used for reaction of an epoxy resin and (meth) acrylic acid can be used. A polymer-supported basic catalyst in which a basic catalyst is supported on a polymer can also be used.

  As described above, the liquid crystal sealant composition of the present invention can contain various compounds H. When the curable resin of the present invention does not contain an ethylenically unsaturated group, the compound As H, the compound which has the above-mentioned ethylenically unsaturated group which is a radically polymerizable compound is preferable.

  Moreover, the compound H demonstrated above may be used individually by 1 type, or may be used in combination of 2 or more type.

<Photopolymerization initiator>
The liquid crystal sealing agent composition of the present invention can contain a photopolymerization initiator as a radical generating source when photopolymerizing the compound H, and the curable resin of the present invention. A photoinitiator is not specifically limited, A well-known compound can be used, 1 type may be used individually or may be used in combination of 2 or more type.

  Examples of the photopolymerization initiator include benzoins, acetophenones, benzophenones, thioxanthones, α-acyloxime esters, phenylglyoxylates, benzyls, azo compounds, diphenyl sulfide compounds, acylphosphine oxide compounds, Examples thereof include benzoin ethers and anthraquinones, and preferably have a reactive group that has low solubility in liquid crystals and that itself does not gasify a decomposition product upon irradiation with light.

<Photosensitizer>
The liquid crystal sealant composition of the present invention is usually photocured, but may contain a photosensitizer in order to increase sensitivity to light at that time. As the photosensitizer, conventionally known various compounds can be used without particular limitation, and the photosensitizer may be used alone or in combination of two or more.

  Examples of the photosensitizer include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreductive dyes from the viewpoint of curability.

  Specific examples of the photosensitizer include an acridone derivative such as N-methylacridone and N-butylacridone; in addition, α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compound and the like. Some of the above photopolymerization initiators function as photosensitizers.

<Curing agent>
From the viewpoint of enhancing the adhesiveness of the liquid crystal sealant composition of the present invention, the liquid crystal sealant composition may contain a curing agent. The said hardening | curing agent is not specifically limited, A well-known compound can be used.

  As the curing agent, amine-based curing agents such as organic acid dihydrazide compounds, imidazole and derivatives thereof, dicyandiamide, aromatic amines, epoxy-modified polyamines, polyaminoureas and the like are preferable from the viewpoint of adhesiveness. These curing agents may be used alone or in combination of two or more.

<Curing accelerator>
The liquid crystal sealing agent composition of the present invention can contain a curing accelerator from the viewpoint of accelerating the curing reaction of the curing component (the curable resin of the present invention or the compound H described above), and the curing accelerator is 1 One species may be used alone, or two or more species may be used in combination.

  Preferred examples thereof include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol and 1,8-diazabicyclo [5.4. 0] Tertiary amines such as undec-7-ene (DBU); phosphines such as triphenylphosphine; metal compounds such as tin octylate.

<Filler>
The liquid crystal sealing agent composition of the present invention can contain a filler from the viewpoint of viscosity control, adhesion reliability, and suppression of linear expansion. As said filler, an inorganic filler and an organic filler can be used, These may be used individually by 1 type, or may be used in combination of 2 or more type.

  As the inorganic filler, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titanium oxide, alumina, zinc oxide, silicon dioxide, kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, and nitriding Silicon etc. are mentioned.

  Examples of the organic filler include polymethyl methacrylate, polystyrene, copolymers obtained by copolymerizing these monomers and other monomers, polyester fine particles, polyurethane fine particles, rubber fine particles, and copolymers having a high glass transition temperature. Examples thereof include core-shell type particles composed of a shell containing a polymer and a copolymer core having a low glass transition temperature. Examples of the core-shell type particles include Zefiac series (F351 etc.) manufactured by Gantz Kasei.

  From the viewpoint of reducing outgas from the liquid crystal sealant by blending a filler that is a non-reactive component, the average particle size of the particles constituting the filler is usually 0.1 to 3 μm, more preferably 0.5. ~ 3 μm. The average particle size of the filler is measured with a laser diffraction / scattering particle size distribution measuring device (for example, Partica LA-950V2 manufactured by HORIBA) manufactured by HORIBA.

<Silane coupling agent>
The liquid crystal sealing agent composition of the present invention can contain a silane coupling agent within the range that exhibits the effects of the present invention. A silane coupling agent may be used individually by 1 type, or may be used in combination of 2 or more type.

From the viewpoint of achieving both the adhesion and flexibility of the cured liquid crystal sealant obtained by curing the liquid crystal sealant composition of the present invention, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetra Tetraalkoxysilanes such as isopropoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane, dimethoxydiisopropoxysilane, diethoxydiisopropoxysilane, diethoxydibutoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltri Isopropoxysilane, ethyltriethoxysilane, ethyltributoxysilane, cyclohexyltriethoxysilane, phenyltriisopropoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane And trialkoxysilanes such as 3-methacryloxypropyltrimethoxysilane; and dialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diethyldibutoxysilane, and phenylethyldiethoxysilane. At least one silane coupling agent selected from the group is preferred,
Among these, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltriethoxysilane, ethyltributoxysilane, cyclohexyltriethoxysilane, phenyltriisopropoxysilane, vinyltrimethoxysilane, 3-glycid More preferably, at least one trialkoxysilane-based silane coupling agent selected from the group consisting of xylpropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane,
3-Glycidoxypropyltrimethoxysilane is more preferred.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, the compound used by the Example and the comparative example was manufactured as follows.

[Comparative Synthesis Example 1] Partially methacrylated bisphenol A type epoxy resin 340.0 g of bisphenol A type epoxy resin (EXA850CRP, manufactured by DIC Corporation), 90.4 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), triphenylphosphine (Tokyo Chemical Industry Co., Ltd.) 0.5 g) and 100 mg of BHT (dibutylhydroxytoluene) were mixed and stirred at 100 ° C. for 6 hours. 418.0 g of partially methacrylated bisphenol A type epoxy resin of a pale yellow transparent viscous product was obtained.

[Synthesis Example 1] Methacrylate curable resin 1
(1) 2000.0 g (4.0 equivalents / hydroxyl group) of polyethylene glycol # 1000 (manufactured by LION), 2220.0 g (6.0 equivalents) of epichlorohydrin, 74.3 g (0.10) of benzyltrimethylammonium chloride Equivalent weight) was placed in a 5 liter three-necked round bottom flask equipped with a mechanical stirrer, thermometer, temperature controller, condenser, Dean-Stark trap and dropping funnel.

  The mixture was then heated to about 50-60 ° C. with stirring under a high vacuum of 50 torr to vigorously reflux epichlorohydrin. 600.0 g of 48% aqueous NaOH was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture.

  Stirring was continued for 3 hours after the addition. Next, the reaction mixture was cooled to room temperature, 3 L of chloroform was added, and the mixture was washed 6 times with 3 L of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure, and 1150.0 g of white waxy solid compound E-1 was obtained.

  (2) Compound E-1 (950.0 g (1.7 equivalents / epoxy group)) and bisphenol A (988.0 g (2.5 equivalents)) are placed in an eggplant type flask, and the liquid temperature becomes 150 ° C. The mixture was stirred with heating. 2.9 g of 4% NaOH aqueous solution was added and stirred at 150 ° C. for 6 hours.

  The solution was cooled to 60 ° C. or lower, 2 L of chloroform was added, washed 6 times with 2 L of 1% NaOH aqueous solution, and washed 6 times with 2 L of water.

  Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is separated by filtration, etc., and the solvent of the obtained organic phase is distilled off under reduced pressure to give a synthetic intermediate as a pale yellow transparent viscous product As a result, 997.0 g of the reaction product G-1 was obtained.

  (3) Reactant G-1 (997.0 g), epichlorohydrin (1423.0 g), and benzyltrimethylammonium chloride (47.5 g) were added to a mechanical stirrer, thermometer, temperature controller, condenser, Dean- Placed in a 5 liter three-necked round bottom flask equipped with a Stark trap and dropping funnel.

  The mixture was then heated to about 50-60 ° C. with stirring under a high vacuum of 50 torr to vigorously reflux epichlorohydrin. 384.0 g of 48% aqueous NaOH was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. Stirring was continued for 3 hours after the addition.

  The reaction mixture was then cooled to room temperature, 2 L of chloroform was added, and the mixture was washed 6 times with 2 L of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 982.0 g of pale yellow viscous resin 1.

  (4) 100.0 g of resin 1, 8.6 g of methacrylic acid, 0.5 g of triphenylphosphine, and 20 mg of BHT were mixed and stirred at 100 ° C. for 5 hours. 107.0g of methacrylic curable resin 1 of the pale yellow viscous thing was obtained.

[Synthesis Example 2] Methacrylate curable resin 2
(1) 500.0 g (1.0 equivalent / hydroxyl group) of polytetramethylene ether glycol (PTMG) 1000 (manufactured by Mitsubishi Chemical Corporation), 555.0 g (6.0 equivalents) of epichlorohydrin, benzyltrimethylammonium chloride 18 .6 g (0.10 eq) was placed in a 2 liter three-necked round bottom flask equipped with a mechanical stirrer, thermometer, temperature controller, condenser, Dean-Stark trap and dropping funnel.

  The mixture was then heated to about 50-60 ° C. with stirring under a high vacuum of 50 torr to vigorously reflux epichlorohydrin. 150.0 g of 48% aqueous NaOH was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. Stirring was continued for 3 hours after the addition.

  The reaction mixture was then cooled to room temperature, 1 L of chloroform was added, and the mixture was washed 4 times with 1 L of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 459.0 g of white waxy solid compound E-2.

  (2) Compound E-2 (132.0 g (0.20 equivalent / epoxy group)) and bisphenol A (114.0 g (2.5 equivalent)) are placed in an eggplant-shaped flask, and the liquid temperature becomes 150 ° C. The mixture was stirred with heating. 0.3 g of 4% NaOH aqueous solution was added and stirred at 150 ° C. for 6 hours. The solution was cooled to a temperature of 60 ° C. or lower, added with 500 mL of chloroform, washed with 1 L of 1% NaOH aqueous solution three times, and washed with 1 L of water three times.

  Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is separated by filtration, etc., and the solvent of the obtained organic phase is distilled off under reduced pressure to give a synthetic intermediate as a pale yellow transparent viscous product 140.0 g of the reaction product G-2 was obtained.

  (3) Reactant G-2 (140.0 g), epichlorohydrin (195.0 g), and benzyltrimethylammonium chloride (6.5 g) were mixed with a mechanical stirrer, thermometer, temperature controller, condenser, Dean- Placed in a 1 liter three-necked round bottom flask equipped with a Stark trap and dropping funnel.

  The mixture was then heated to about 50-60 ° C. with stirring under a high vacuum of 50 torr to vigorously reflux epichlorohydrin. 53.0 g of 48% aqueous NaOH was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. Stirring was continued for 3 hours after the addition. Next, the reaction mixture was cooled to room temperature, 500 mL of chloroform was added, and the mixture was washed 4 times with 500 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 129.0 g of light yellow viscous resin 2.

  (4) 48.6 g of resin 2, 4.3 g of methacrylic acid, 0.3 g of triphenylphosphine, and 10 mg of BHT were mixed and stirred at 100 ° C. for 6 hours. 50.6g of methacryl-ized curable resin 2 of the pale yellow viscous thing was obtained.

[Synthesis Example 3] Methacrylate curable resin 3
(1) 350.0 g (0.50 equivalent / hydroxyl group) of NISSO-PB G-1000 (manufactured by Nippon Soda Co., Ltd.), 370.0 g (8.0 equivalents) of epichlorohydrin, 9.3 g of benzyltrimethylammonium chloride ( 0.10 equivalents) was placed in a 2 liter three-necked round bottom flask equipped with a mechanical stirrer, thermometer, temperature controller, condenser, Dean-Stark trap and dropping funnel.

  The mixture was then heated to about 50-60 ° C. with stirring under a high vacuum of 50 torr to vigorously reflux epichlorohydrin. 75.0 g of 48% aqueous NaOH was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. Stirring was continued for 3 hours after the addition.

  Next, the reaction mixture was cooled to room temperature, 500 mL of chloroform was added, and the mixture was washed 6 times with 500 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 298.0 g of transparent viscous compound E-3.

  (2) Compound E-3 (96.5 g (0.10 equivalent / epoxy group)), bisphenol A (68.5 g (3.0 equivalent)), 0.9 g (0.050 equivalent) of benzyltrimethylammonium chloride and 100.0 g of methyl isobutyl ketone was placed in an eggplant type flask, and stirred for 20 hours while heating and refluxing so that the liquid temperature became 120 ° C. The solution was cooled to a temperature of 60 ° C. or lower, added with 300 mL of chloroform, washed 5 times with 300 mL of 1% NaOH aqueous solution, and 5 times with 300 mL of water.

  Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is separated by filtration, etc., and the solvent of the obtained organic phase is distilled off under reduced pressure to give a synthetic intermediate as a pale yellow transparent viscous product As a result, 75.5 g of the reaction product G-3 was obtained.

  (3) Reactant G-3 (75.5 g), epichlorohydrin (112.5 g), and benzyltrimethylammonium chloride (2.8 g) were mixed with a mechanical stirrer, thermometer, temperature controller, condenser, Dean- Place in a 500 ml three-necked round bottom flask equipped with a Stark trap and dropping funnel.

  The mixture was then heated to about 50-60 ° C. with stirring under a high vacuum of 50 torr to vigorously reflux epichlorohydrin. 23.0 g of 48% aqueous NaOH was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. Stirring was continued for 3 hours after the addition.

  Subsequently, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and the mixture was washed 6 times with 300 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 54.4 g of light yellow viscous resin 3.

  (4) 50.0 g of resin 3, 3.3 g of methacrylic acid, 0.2 g of triphenylphosphine, and 10 mg of BHT were mixed and stirred at 100 ° C. for 5 hours. 47.0g of methacryl-ized curable resin 3 of the pale yellow viscous thing was obtained.

[Synthesis Example 4] Methacrylate curable resin 4
(1) NISSO-PB GI-1000 (Nippon Soda Co., Ltd.) 300.0 g (0.40 equivalent / hydroxyl group), epichlorohydrin 296.0 g (8.0 equivalent), benzyltrimethylammonium chloride 7.4 g ( 0.10 equivalents) was placed in a 2 liter three-necked round bottom flask equipped with a mechanical stirrer, thermometer, temperature controller, condenser, Dean-Stark trap and dropping funnel.

  The mixture was then heated to about 50-60 ° C. with stirring under a high vacuum of 50 torr to vigorously reflux epichlorohydrin. 60.0 g of 48% aqueous NaOH was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. Stirring was continued for 3 hours after the addition.

  Next, the reaction mixture was cooled to room temperature, 500 mL of chloroform was added, and the mixture was washed 6 times with 500 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 264.0 g of transparent viscous compound E-4.

  (2) Compound E-4 (80.0 g (0.060 eq / epoxy group)), bisphenol A (57.1 g (4.0 eq)), benzyltrimethylammonium chloride 0.9 g (0.080 eq) and 100.0 g of methyl isobutyl ketone was placed in an eggplant type flask, and stirred for 20 hours while heating and refluxing so that the liquid temperature became 120 ° C. The solution was cooled to a temperature of 60 ° C. or lower, added with 300 mL of chloroform, washed 5 times with 300 mL of 1% NaOH aqueous solution, and 5 times with 300 mL of water.

  Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is separated by filtration, etc., and the solvent of the obtained organic phase is distilled off under reduced pressure to give a pale yellow viscous product as a synthetic intermediate. 80.0 g of a certain reactant G-4 was obtained.

  (3) Reactant G-4 (80.0 g), epichlorohydrin (88.8 g), and benzyltrimethylammonium chloride (3.0 g) were mixed with a mechanical stirrer, thermometer, temperature controller, condenser, Dean- Place in a 500 ml three-necked round bottom flask equipped with a Stark trap and dropping funnel.

  The mixture was then heated to about 50-60 ° C. with stirring under a high vacuum of 50 torr to vigorously reflux epichlorohydrin. 24.0 g of 48% aqueous NaOH was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. Stirring was continued for 3 hours after the addition.

  Subsequently, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and the mixture was washed 6 times with 300 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 56.0 g of light yellow viscous resin 4.

  (4) 50.0 g of resin 4, 3.0 g of methacrylic acid, 0.2 g of triphenylphosphine, and 10 mg of BHT were mixed and stirred at 100 ° C. for 12 hours. 47.0g of methacryl-ized curable resin 4 of the pale yellow viscous thing was obtained.

[Synthesis Example 5] Methacrylate curable resin 5
(1) Compound E-2 (96.0 g (0.15 equivalent / epoxy group)), 4-α-cumylphenol (30.0 g (1.0 equivalent)), benzyltrimethylammonium chloride 1.4 g (0 .050 equivalents) was placed in an eggplant-shaped flask and stirred for 30 hours while heating to reflux so that the liquid temperature was 120 ° C. It cooled until liquid temperature became 60 degrees C or less, and obtained 125.0g of reactant G-5 which is a synthetic intermediate as a pale yellow viscous substance.

  (2) Reactant G-5 (125.0 g), epichlorohydrin (150.0 g), and benzyltrimethylammonium chloride (2.8 g) were mixed with a mechanical stirrer, thermometer, temperature controller, condenser, Dean- Place in a 500 ml three-necked round bottom flask equipped with a Stark trap and dropping funnel.

  The mixture was then heated to about 50-60 ° C. with stirring under a high vacuum of 50 torr to vigorously reflux epichlorohydrin. 30.0 g of 48% aqueous NaOH was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. Stirring was continued for 3 hours after the addition.

  Next, the reaction mixture was cooled to room temperature, 500 mL of chloroform was added, and the mixture was washed 6 times with 500 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 130.0 g of pale yellow viscous resin 5.

  (3) 63.5 g of resin 5, 4.3 g of methacrylic acid, 0.1 g of triphenylphosphine, and 13 mg of BHT were mixed and stirred at 100 ° C. for 6 hours. 66.0g of methacryl-ized curable resin 5 of the pale yellow viscous thing was obtained.

[Synthesis Example 6] Methacrylate curable resin 6
(1) Compound E-2 (64.0 g (0.10 equivalent / epoxy group)) and resorcinol (27.5 g (2.5 equivalent)) are placed in an eggplant-shaped flask so that the liquid temperature becomes 120 ° C. The mixture was stirred with heating. 0.2 g of 4% NaOH aqueous solution was added, and the mixture was stirred at 120 ° C. for 24 hours. It cooled until the liquid temperature became 60 degrees C or less, 300 mL of chloroform was added, and it wash | cleaned 4 times with 300 mL of water.

  Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is separated by filtration, etc., and the solvent of the obtained organic phase is distilled off under reduced pressure to give a synthetic intermediate as a pale yellow transparent viscous product As a result, 60.5 g of the reaction product G-6 was obtained.

  (2) Reactant G-6 (60.5 g), epichlorohydrin (102.0 g), and benzyltrimethylammonium chloride (3.4 g) were added to a mechanical stirrer, thermometer, temperature controller, condenser, Dean- Place in a 500 ml three-necked round bottom flask equipped with a Stark trap and dropping funnel.

  The mixture was then heated to about 50-60 ° C. with stirring under a high vacuum of 50 torr to vigorously reflux epichlorohydrin. 28.0 g of 48% aqueous NaOH was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. Stirring was continued for 3 hours after the addition. Subsequently, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and the mixture was washed 6 times with 300 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 48.0 g of light yellow viscous resin 6.

  (3) 44.6 g of resin 6, 4.3 g of methacrylic acid, 0.1 g of triphenylphosphine, and 10 mg of BHT were mixed and stirred at 100 ° C. for 14 hours. 42.8g of methacryl-ized curable resin 6 of the pale yellow viscous thing was obtained.

[Synthesis Example 7] Methacrylate curable resin 7
(1) Compound E-2 (53.0 g (0.080 equivalent / epoxy group)) and 2- (4-hydroxyphenyl) ethanol (11.1 g (1.0 equivalent)) were placed in an eggplant-shaped flask, The mixture was heated and stirred so that the liquid temperature became 120 ° C. Benzyltrimethylammonium chloride (3.0 g (0.20 equivalent)) was added and stirred at 120 ° C. for 24 hours. It cooled until the liquid temperature became 60 degrees C or less, chloroform 300mL was added, and it wash | cleaned once with 300 mL of 1% NaOH aqueous solution, and 5 times with 300 mL of water.

  Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is separated by filtration, etc., and the solvent of the obtained organic phase is distilled off under reduced pressure to give a synthetic intermediate as a pale yellow transparent viscous product As a result, 59.0 g of the reaction product G-7 was obtained.

  (2) Reactant G-7 (59.0 g), epichlorohydrin (93.3 g), and benzyltrimethylammonium chloride (3.1 g) were stirred with a mechanical stirrer, thermometer, temperature controller, condenser, Dean- Place in a 500 ml three-necked round bottom flask equipped with a Stark trap and dropping funnel.

  The mixture was then heated to about 50-60 ° C. with stirring under a high vacuum of 50 torr to vigorously reflux epichlorohydrin. 25.2 g of 48% aqueous NaOH was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. Stirring was continued for 3 hours after the addition. Subsequently, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and the mixture was washed 6 times with 300 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 50.5 g of a pale yellow viscous resin 7.

  (3) 47.3 g of resin 7, 5.2 g of methacrylic acid, 0.1 g of triphenylphosphine, and 10 mg of BHT were mixed and stirred at 100 ° C. for 7 hours. 51.0g of methacryl-ized curable resin 7 of the pale yellow viscous thing was obtained.

[Synthesis Example 8] Methacrylate curable resin 8
(1) Compound E-2 (94.0 g (0.15 equivalent / epoxy group)) and phenol (21.2 g (1.5 equivalent)) are placed in an eggplant type flask so that the liquid temperature becomes 120 ° C. The mixture was stirred with heating. Benzyltrimethylammonium chloride (2.8 g (0.10 equivalent)) was added and stirred at 120 ° C. for 24 hours. The solution was cooled to a temperature of 60 ° C. or lower, added with 300 mL of methyl isobutyl ketone, washed twice with 300 mL of 1% NaOH aqueous solution, and washed with 300 mL of water four times.

  Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is separated by filtration, etc., and the solvent of the obtained organic phase is distilled off under reduced pressure to give a synthetic intermediate as a pale yellow transparent viscous product As a result, 90.0 g of the reaction product G-8 was obtained.

  (2) Reactant G-8 (90.0 g), epichlorohydrin (130.0 g), and benzyltrimethylammonium chloride (2.6 g) were mixed with a mechanical stirrer, thermometer, temperature controller, condenser, Dean- Place in a 500 ml three-necked round bottom flask equipped with a Stark trap and dropping funnel.

  The mixture was then heated to about 50-60 ° C. with stirring under a high vacuum of 50 torr to vigorously reflux epichlorohydrin. 21.0 g of 48% aqueous NaOH was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. Stirring was continued for 3 hours after the addition. Subsequently, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and the mixture was washed 6 times with 300 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 80 g of a pale yellow viscous resin 8.

  (3) 57.6 g of resin 8, 3.5 g of methacrylic acid, 0.1 g of triphenylphosphine, and 10 mg of BHT were mixed and stirred at 100 ° C. for 13 hours. 59.2g of methacrylic curable resin 8 of pale yellow viscous material was obtained.

[Synthesis Example 9] Methacrylate curable resin 9
(1) Compound E-2 (63.0 g (0.10 equivalent / epoxy group)) and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (95.0 g (2.5 equivalent)) 1-butanol (80.0 g) was placed in an eggplant-shaped flask and heated to reflux at 120 ° C. Benzyltrimethylammonium chloride (0.9 g (0.050 equivalent)) was added and stirred at 120 ° C. for 20 hours. It cooled until the liquid temperature became 60 degrees C or less, chloroform 300mL was added, it wash | cleaned 14 times with 300 mL of 1% NaOH aqueous solution, and 5 times with 300 mL of water.

  Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is separated by filtration, etc., and the solvent of the obtained organic phase is distilled off under reduced pressure to give a synthetic intermediate as a pale yellow transparent viscous product As a result, 56.0 g of the reaction product G-9 was obtained.

  (2) Reactant G-9 (56.0 g), epichlorohydrin (111.0 g), and benzyltrimethylammonium chloride (2.2 g) were stirred with a mechanical stirrer, thermometer, temperature controller, condenser, Dean- Place in a 500 ml three-necked round bottom flask equipped with a Stark trap and dropping funnel.

  The mixture was then heated to about 50-60 ° C. with stirring under a high vacuum of 50 torr to vigorously reflux epichlorohydrin. 18.0 g of 48% aqueous NaOH was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. Stirring was continued for 3 hours after the addition. Subsequently, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and the mixture was washed 6 times with 300 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 54.0 g of light yellow viscous resin 9.

  (3) 51.0 g of resin 9, 4.3 g of methacrylic acid, 0.1 g of triphenylphosphine, and 10 mg of BHT were mixed and stirred at 100 ° C. for 9 hours. 49.8g of methacryl-ized curable resin 9 of the pale yellow viscous thing was obtained.

[Synthesis Example 10] Methacrylate curable resin 10
(1) 1000.0 g (1.0 equivalent / hydroxyl group) of PEG-2000 (manufactured by Toho Chemical Industry Co., Ltd.), 925.0 g (10 equivalents) of epichlorohydrin, 18.6 g (0.10 equivalents) of benzyltrimethylammonium chloride ) In a 5 liter three-necked round bottom flask equipped with a mechanical stirrer, thermometer, temperature controller, condenser, Dean-Stark trap and dropping funnel.

  The mixture was then heated to about 50-60 ° C. with stirring under a high vacuum of 50 torr to vigorously reflux epichlorohydrin. 150.0 g of 48% aqueous NaOH was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture.

  Stirring was continued for 3 hours after the addition. The reaction mixture was then cooled to room temperature, 1 L of chloroform was added, and the mixture was washed 3 times with 1 L of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 760.0 g of a white waxy solid compound E-5.

  (2) Compound E-5 (220.0 g (0.20 equivalent / epoxy group)) and bisphenol A (31.0 g (1.4 equivalent)) are placed in an eggplant-shaped flask, and the liquid temperature becomes 110 ° C. The mixture was stirred with heating. 1.9 g of benzyltrimethylammonium chloride was added and stirred at 110 ° C. for 20 hours.

  It cooled until the liquid temperature became 60 degrees C or less, chloroform 300mL was added, it wash | cleaned 3 times with 300 mL of 1% NaOH aqueous solution, and 6 times with 300 mL of water.

  Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is separated by filtration, etc., and the solvent of the obtained organic phase is distilled off under reduced pressure to give a synthetic intermediate as a pale yellow transparent viscous product 110.0 g of the reaction product G-10 was obtained.

  (3) Reactant G-10 (108.0 g), epichlorohydrin (175.0 g), and benzyltrimethylammonium chloride (2.3 g) were mixed with a mechanical stirrer, thermometer, temperature controller, condenser, Dean- Placed in a 1 liter three-necked round bottom flask equipped with a Stark trap and dropping funnel.

  The mixture was then heated to about 50-60 ° C. with stirring under a high vacuum of 50 torr to vigorously reflux epichlorohydrin. 19.0 g of 48% aqueous NaOH was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. Stirring was continued for 3 hours after the addition.

  Subsequently, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and the mixture was washed 6 times with 300 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 92.0 g of white waxy resin 10.

  (4) 21.7 g of resin 10, 1.1 g of methacrylic acid, 0.1 g of benzyltrimethylammonium chloride, 50.0 g of toluene, and 15 mg of BHT were mixed and stirred at 100 ° C. for 7 hours. The reaction mixture was then cooled to room temperature, added with 100 mL of chloroform, and washed 3 times with 100 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 17.0 g of a white waxy solid methacrylic curable resin 10.

[Synthesis Example 11] Methacrylate curable resin 11
(1) 500.0 g (0.50 equivalent / hydroxyl group) of polytetramethylene ether glycol (PTMG) 2000 (manufactured by Mitsubishi Chemical Corporation), 463.0 g (10 equivalents) of epichlorohydrin, 9.3 g of benzyltrimethylammonium chloride (0.10 equivalent) was placed in a 2 liter three-necked round bottom flask equipped with a mechanical stirrer, thermometer, temperature controller, condenser, Dean-Stark trap and dropping funnel.

  The mixture was then heated to about 50-60 ° C. with stirring under a high vacuum of 50 torr to vigorously reflux epichlorohydrin. 75.0 g of 48% aqueous NaOH was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture.

  Stirring was continued for 3 hours after the addition. The reaction mixture was then cooled to room temperature, 1 L of chloroform was added, and the mixture was washed 3 times with 1 L of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 450.0 g of white waxy solid compound E-6.

  (2) Compound E-6 (127.0 g (0.10 equivalent / epoxy group)) and bisphenol A (15.0 g (1.4 equivalent)) are placed in an eggplant type flask, and the liquid temperature becomes 110 ° C. The mixture was stirred with heating. 0.9 g of benzyltrimethylammonium chloride was added and stirred at 110 ° C. for 20 hours.

  It cooled until the liquid temperature became 60 degrees C or less, chloroform 300mL was added, it wash | cleaned 3 times with 300 mL of 1% NaOH aqueous solution, and 6 times with 300 mL of water.

  Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is separated by filtration, etc., and the solvent of the obtained organic phase is distilled off under reduced pressure to give a synthetic intermediate as a pale yellow transparent viscous product As a result, 120.0 g of the reaction product G-11 was obtained.

  (3) Reactant G-11 (117.0 g), epichlorohydrin (125.0 g), and benzyltrimethylammonium chloride (2.5 g) were added to a mechanical stirrer, thermometer, temperature controller, condenser, Dean- Placed in a 1 liter three-necked round bottom flask equipped with a Stark trap and dropping funnel.

  The mixture was then heated to about 50-60 ° C. with stirring under a high vacuum of 50 torr to vigorously reflux epichlorohydrin. 20.0 g of 48% aqueous NaOH was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. Stirring was continued for 3 hours after the addition.

  Subsequently, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and the mixture was washed 6 times with 300 mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 92.0 g of a pale yellow viscous resin 11.

  (4) 55.0 g of resin 11, 2.6 g of methacrylic acid, 0.1 g of triphenylphosphine, and 10 mg of BHT were mixed and stirred at 100 ° C. for 7 hours. 54.0g of methacryl-ized curable resin 11 of the pale yellow viscous thing was obtained.

[Production of photopolymerization initiator]
The photopolymerization initiator used in Examples and Comparative Examples was produced as follows.

<Production of photopolymerization initiator 1>
Denacol EX-830 (PEG 400 diglycidyl ether manufactured by Nagase ChemteX) 26.8 g (0.10 equivalent / epoxy group), 4-dimethylaminobenzoic acid 16.5 g (1.0 equivalent), benzyltrimethylammonium chloride 3 0.7 g (0.20 equivalent) and MIBK (methyl isobutyl ketone) 25.0 g were placed in a flask and stirred at 110 ° C. for 24 hours. The reaction mixture was cooled to room temperature, dissolved in 50 g of chloroform, and washed 6 times with 100 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 35.3 g of photopolymerization initiator 1.

<Production of photopolymerization initiator 2>
Denacol EX-830 (PEG 400 diglycidyl ether manufactured by Nagase ChemteX) 26.8 g (0.10 equivalent / epoxy group), 2-hydroxy-9H-thioxanthen-9-one 22.8 g (1.0 equivalent) , Benzyltrimethylammonium chloride 3.7 g (0.20 equivalent) and MIBK 40.0 g were placed in a flask and stirred at 110 ° C. for 72 hours. The reaction mixture was cooled to room temperature, dissolved in 50 g of chloroform, and washed 6 times with 100 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 36.2 g of photopolymerization initiator 2.

[Examples 1 to 11 and Comparative Example 1]
Each of the partially methacrylated bisphenol A type epoxy resins and methacrylated curable resins 1 to 11 produced in the synthesis examples and comparative synthesis examples, photopolymerization initiators 1 and 2, and EH-5030S (made by ADEKA ( The polyamine compound)) was mixed in the blending amounts (parts by weight) shown in Table 1 below, and then sufficiently kneaded using a three-roll mill (C-43 / 4 × 10 manufactured by Inoue Seisakusho). 1-11 and the liquid-crystal sealing compound composition of the comparative example 1 were obtained.

  The following tests evaluated the each compound manufactured by the synthesis example and the comparative synthesis example, and each of these liquid-crystal sealing compound compositions.

[Test conditions]
For the partially methacrylated bisphenol A type epoxy resin and the methacrylated curable resins 1 to 9 and 11, the epoxy equivalent, viscosity and NI point change were measured,
For the methacrylic curable resin 10, the epoxy equivalent and NI point change are measured,
For photoinitiators 1 and 2, the viscosity and NI point change are measured,
For the curing agent (EH-5030S), measure the NI point change,
The Tg of the cured product of the liquid crystal sealant composition produced in Examples 1 to 11 and Comparative Example 1 and the storage elastic modulus at various temperatures were measured.

(1) Epoxy equivalent measurement It measured on the conditions of JISK7236: 2001.

(2) Viscosity measurement It measured at 25 degreeC using the E-type viscosity meter (TO105 Sangyo Co., Ltd. RE105U).
The rotor and the number of rotations were selected as follows.

Partially methacrylated bisphenol A type epoxy resin: 3 ° × R7.7 rotor, rotation speed 10 rpm
Methacrylic curable resin 1: 3 ° × R7.7 rotor, rotation speed 15 rpm
Methacrylic curable resin 2: 3 ° × R7.7 rotor, rotation speed 15 rpm
Methacrylic curable resin 3: 3 ° × R7.7 rotor, rotation speed 0.5 rpm
Methacrylic curable resin 4: 3 ° × R7.7 rotor, rotation speed 0.2 rpm
Methacrylate curable resin 5: 1 ° 34 ′ × R24 rotor, rotation speed 2.0 rpm
Methacrylic curable resin 6: 3 ° × R14 rotor, rotation speed 5.0 rpm
Methacrylic curable resin 7: 1 ° 34 ′ × R24 rotor, rotation speed 5.0 rpm
Methacrylic curable resin 8: 1 ° 34 '× R24 rotor, rotation speed 2.0rpm
Methacrylic curable resin 9: 3 ° × R7.7 rotor, rotation speed 2.0 rpm
Methacrylic curable resin 11: 3 ° × R7.7 rotor, rotation speed 15 rpm

(3) NI point change measurement 0.1 g of each of partially methacrylated bisphenol A type epoxy resin, methacrylated curable resins 1 to 11, photopolymerization initiators 1 and 2, and curing agent (EH-5030S) are put into an ampule bottle. Furthermore, 1 g of liquid crystal (MLC-11900-080, manufactured by Merck & Co., Inc.) was added. This bottle was placed in a 120 ° C. oven for 1 hour, and then allowed to stand at room temperature. After returning to room temperature (25 ° C.), the liquid crystal portion was taken out and filtered through a 0.2 μm filter to obtain a liquid crystal sample for evaluation.

  The NI point was measured using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer, PYRIS6), 10 mg of a liquid crystal sample for evaluation was enclosed in an aluminum sample pan, and the temperature rising rate was 5 ° C./min. . In addition, 10 mg of the liquid crystal was sealed in an aluminum sample pan, and a measurement was performed under a temperature rising rate of 5 ° C./min.

  The difference TE-TB between the blank endothermic peak top (phase transition temperature) TB and the endothermic peak top (phase transition temperature) TE of the liquid crystal for evaluation was defined as the NI point change. From the viewpoints of suppressing the elution of the components contained in the liquid crystal sealant into the liquid crystal, ensuring stable alignment of the liquid crystal, and improving the display characteristics, the absolute value of the NI point change is preferably as small as possible.

(4) Tg measurement About the liquid-crystal sealing compound composition manufactured in Examples 1-11 and the comparative example 1, it casts into a type | mold of length 5cm, width 5mm, and thickness 0.5mm, and ultraviolet-ray (UV irradiation apparatus: UVX). -01224S1, Ushio Inc., was cured by irradiation with 100 mW ^/ cm 2 / integrating the 30 seconds) at 365nm amount 3000 mJ / cm ^2, then for 1 hour thermoset at 120 ° C. in a hot air oven, the cured product test Created a piece.

  The obtained cured product test piece was measured with a dynamic viscoelasticity measuring apparatus (DMA, manufactured by Seiko Instruments Inc., DMS6100), with the deformation mode as tension, at a frequency of 1.0 Hz, in the range of −50 ° C. to 100 ° C. The measurement was performed while raising the temperature at ° C / min. The peak top temperature at the loss tangent tan δ obtained as a result was defined as Tg.

(5) Storage elastic modulus measurement About the liquid crystal sealing agent composition manufactured in Examples 1-11 and Comparative Example 1, creation of a cured product test piece and dynamic viscoelasticity measuring apparatus (DMA, Seiko Inn under the same conditions as Tg) Measurement was performed using DMS6100 (manufactured by Stulu). In the obtained results, the value of the storage elastic modulus at each temperature was extracted.

  The results of the above evaluation are shown in Table 1 below together with the blending compositions of the liquid crystal sealant compositions of Examples 1 to 11 and Comparative Example 1.

Claims (6)

Curable resin represented by the following formula (1):

[Wherein m is a number in the range of 1-7,
X is independently of each other a hydrogen atom, a hydroxyl group, a glycidyloxy group, or a methylglycidyloxy group,
R ^{1 s} are each independently a hydrogen atom, a glycidyl group or a methyl glycidyl group,
R ^{2 s} are each independently a hydrogen atom or a methyl group,
A ring is a group containing 5 or more carbon atoms and a total number of heteroatoms independently of each other and containing one or more aromatic rings or heteroaromatic rings,
Y represents the following formula (1a):

(Wherein Y ¹ are each independently an alkylene group having 2 to 5 carbon atoms, and n is a number in the range of 1 to 250), the following formula (1b):

Wherein Y ² is a direct bond or an alkylene group having 1 or 2 carbon atoms, independently of each other, R ³ is a hydrogen atom or a methyl group, independently of each other, and p and q are each independently 0 And the total number thereof is a number in the range of 1 to 200), or a group having a structure in which part or all of the unsaturated bonds in the formula (1b) are hydrogenated,
Regarding R ¹ and X, the average x of the total number of R ¹ that is a glycidyl group or a methyl glycidyl group and X that is a glycidyloxy group or a methyl glycidyloxy group is 1 or more. ].   In said Formula (1), the carbon atom number contained in A ring is 4-40, an oxygen atom number is 0-5, a nitrogen atom number is 0-5, and a sulfur atom number is 0-5. The curable resin according to claim 1, wherein the number of ring structures contained in the A ring is 1 to 5.   (Meth) obtained by reacting at least part of the epoxy group, hydroxyl group and unsaturated bond of the curable resin according to claim 1 or 2 with (meth) acrylic acid and / or (meth) acrylic anhydride. Acrylic curable resin.   A liquid crystal sealing agent composition comprising the curable resin according to claim 1 and / or the (meth) acrylated curable resin according to claim 3.   The liquid-crystal sealing compound composition of Claim 4 whose content of curable resin and / or (meth) acrylated curable resin in the said liquid-crystal sealing compound composition is 5-95 weight%.   The liquid crystal sealant composition further comprises a compound H having an ethylenically unsaturated group and / or an epoxy group (excluding the curable resin and the (meth) acrylated curable resin). 5. A liquid crystal sealant composition according to 5.