WO2014057871A1

WO2014057871A1 - Glycidyl ether compound, liquid crystal sealant, and method for producing glycidyl ether compound

Info

Publication number: WO2014057871A1
Application number: PCT/JP2013/077036
Authority: WO
Inventors: 大晃臼井; 良爾堀越; 健介宮崎
Original assignee: 協立化学産業株式会社
Priority date: 2012-10-12
Filing date: 2013-10-04
Publication date: 2014-04-17
Also published as: CN104718231B; KR20150068448A; TWI586695B; TW201428018A; KR102056074B1; JPWO2014057871A1; CN104718231A; JP6310852B2

Abstract

The present invention provides a glycidyl ether compound that scarcely affects liquid crystal molecular alignment and makes it possible for a liquid crystal sealant to adhere strongly and cure even when a liquid crystal sealant is applied in a narrow seal width and bonded to a base in a one-drop-fill method. The present invention also provides a liquid crystal sealant containing the glycidyl ether compound, and a method for producing the glycidyl ether compound.

Description

Glycidyl ether compound, liquid crystal sealant, and method for producing glycidyl ether compound

The present invention relates to a glycidyl ether compound, a liquid crystal sealant containing the glycidyl ether compound, and a method for producing the glycidyl ether compound.

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 either substrate. 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 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 high-speed curing (see, for example, JP-A-2007-297470).

However, in recent years, the demand for small panels has increased due to the widespread use of smartphones and tablet terminals, etc., and panel design with improved design has led to a narrower frame, increasing the demand for thinning of the liquid crystal sealant coating. ing. For example, a level that halves the conventional seal width of 1.0 to 1.5 mm is required. In response to such demands, there has been a need for a liquid crystal sealant that can maintain or improve the adhesive strength from the viewpoint of durability even if the adhesive area is reduced by narrowing the seal width.

In the liquid crystal dripping method, a seal is applied to the base in the form of a frame to form a frame seal, the liquid crystal is dropped inside the frame, vacuum is applied to the panel, and UV irradiation is performed to lightly cure the liquid crystal sealant. After that, heat curing is performed at a temperature equal to or higher than the NI point (Nematic （Isotropic point) of the liquid crystal to thermally cure the liquid crystal sealant and simultaneously align the liquid crystal.

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. Since the liquid crystal sealant was photocured, it was in contact with the liquid crystal because it did not come into contact with the liquid crystal. Alternatively, the contact time between the liquid crystal and the uncured liquid crystal sealant was short.
On the other hand, since the distance from the liquid crystal dropping point to the frame seal is short in the small panel, the liquid crystal sealant comes into contact with the liquid crystal in an uncured state between the bonding and UV irradiation (long contact time). Therefore, the liquid crystal contamination in the uncured state of the liquid crystal sealant becomes a problem than before.

The conventional radical polymerization reactive liquid crystal sealant mainly composed of an epoxy compound containing an epoxy / acrylic compound has not been able to sufficiently meet such a demand.

The problem of the present invention is that the liquid crystal sealing agent can be strongly bonded and cured even when the liquid crystal sealing agent is applied with a narrow seal width and the substrate is bonded in the liquid crystal dropping method, which affects the liquid crystal orientation. It is an object of the present invention to provide a glycidyl ether compound that is difficult to give, a liquid crystal sealant containing the glycidyl ether compound, and a method for producing the glycidyl ether compound.

The present invention includes the following aspects.
[1] The following formula (1):

[Wherein n ₁ is a number in the range of 2-30, m is a number in the range of 1-5,
X is an oxygen atom (O), an alkylene group having 1 to 4 carbon atoms, or an alkylidene group having 2 to 4 carbon atoms,
Y is each independently an alkylene group having 2 to 4 carbon atoms,
R is independently of each other a hydrogen atom, a glycidyl group, a methylglycidyl group, a group 1: —CH ₂ —CH (OR ¹ ) —CH ₂ —O—R ² or a group 2: —CH ₂ —C (CH ₃ ) (OR ¹ ) —CH ₂ —O—R ² (wherein R ¹ is a hydrogen atom or a (meth) acryloyl group, and R ² is a (meth) acryloyl group),
Each R ′, independently of one another, is a hydrogen atom or a methyl group;
In R, the total number x of the total of the glycidyl group, the methyl glycidyl group, the group 1 and the group 2 is 2 or more,
When the R includes the group 1 or the group 2, the ratio of the average number y of the total of the glycidyl group and the methylglycidyl group and the average number z of the total of the group 1 and the group 2 (y / z ) Is 10/90 to 90/10].
[2] A liquid crystal sealant comprising the glycidyl ether compound according to [1].
[3] The following formula (2):

(Where n ₂ is a number in the range of 2-30,
Y is each independently an alkylene group having 2 to 4 carbon atoms,
R ¹¹ is each independently a hydrogen atom, a glycidyl group or a methyl glycidyl group)
Following formula (3):

[Wherein X is an oxygen atom, an alkylene group having 1 to 4 carbon atoms, or an alkylidene group having 2 to 4 carbon atoms,
R ¹² is independently of each other a hydrogen atom, a glycidyl group, a methyl glycidyl group, a group 1: —CH ₂ —CH (OR ²¹ ) —CH ₂ —O—R ²² or a group 2: —CH ₂ —C (CH ₃ ) a compound represented by (OR ²¹ ) —CH ₂ —O—R ²² (wherein R ²¹ is a hydrogen atom or a (meth) acryloyl group, and R ²² is a (meth) acryloyl group). It is a manufacturing method of the glycidyl ether type compound represented by Formula (1) of said [1] description including the process with which D is made to react.

According to the present invention, in the liquid crystal dropping method, even when the liquid crystal sealant is applied with a narrow seal width and the substrate is bonded, the liquid crystal sealant can be strongly bonded and cured, which affects the liquid crystal orientation. It is possible to provide a glycidyl ether compound that is difficult to give, a liquid crystal sealant containing the glycidyl ether compound, and a method for producing the glycidyl ether compound.

It is a microscope image which shows the example (compound A-3) when the liquid crystal aligning property in an Example is (circle). It is a microscope image which shows the example (compound A-5) when the liquid crystal aligning property in an Example is (circle). It is a microscope image which shows the example (compound B) in case the liquid crystal orientation in an Example is x. It is a conceptual diagram which shows the outline | summary of the test method of adhesive strength.

In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. . The numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. The amount of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.
Moreover, (meth) acryloyl means methacryloyl and / or acryloyl, and (meth) acrylate means methacrylate and / or acrylate.

[Compound A]
The glycidyl ether compound of the present invention (hereinafter also referred to as compound A) is represented by the following formula (1).

In the formula, n ₁ is a number in the range of 2 to 30, and m is a number in the range of 1 to 5.
X is an oxygen atom (O), an alkylene group having 1 to 4 carbon atoms, or an alkylidene group having 2 to 4 carbon atoms. Y is each independently an alkylene group having 2 to 4 carbon atoms.
R is independently of each other a hydrogen atom, a glycidyl group, a methylglycidyl group, a group 1: —CH ₂ —CH (OR ¹ ) —CH ₂ —O—R ² or a group 2: —CH ₂ —C (CH ₃ ) (OR ¹ ) —CH ₂ —O—R ² (wherein R ¹ is a hydrogen atom or a (meth) acryloyl group, and R ² is a (meth) acryloyl group). R ′ is, independently of each other, a hydrogen atom or a methyl group.
In R, when the total number x of the total of the glycidyl group, the methyl glycidyl group, the group 1 and the group 2 is 2 or more, and the R includes the group 1 or the group 2, the glycidyl group And the ratio (y / z) of the average number y of the total of the methyl glycidyl groups and the total number z of the total of the groups 1 and 2 is 10/90 to 90/10.

In Compound A, in the liquid crystal dropping method, when the liquid crystal sealant is applied with a narrow seal width and the base is bonded, the liquid crystal sealant strongly adheres and cures (hereinafter also referred to as strong adhesiveness). N ₁ is a number in the range of 3 to 25, preferably a number in the range of 5 to 20, more preferably a number in the range of 5 to 15, more preferably in the range of 7 to 10. Is a number. N ₁ is derived from the number of repeating units of the compound represented by formula (2) (compound C), that is, n ₂ .

From the viewpoint of the application property of the liquid crystal sealing agent in the compound A (for example, the drawing speed and production tact in the dispenser are not reduced) and the compounding property of the liquid crystal sealing agent (the viscosity of the compound A is not excessively increased), m Is a number in the range of 1 to 5, preferably a number in the range of 1 to 4, more preferably a number in the range of 1 to 3, and still more preferably a number in the range of 1 to 2. In addition, m can be estimated from the reaction equivalent ratio (preparation amount) of the compound C and the compound D which are raw materials of the compound A.

Incidentally, _{n 1} and m can also be measured by GPC.

Y is each independently an alkylene group having 2 to 4 carbon atoms, specifically, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, or the like. Y is preferably an ethylene group or a propylene group, and more preferably an ethylene group.

In R in Compound A, the average number x of the total of glycidyl group, methylglycidyl group, group 1 and group 2 is influenced by workability of the liquid crystal sealant such as coating property affected by viscosity, for example, crosslink density. From the viewpoint of physical properties such as strength after curing, it is 2 or more, preferably 2 to 2 m + 2, more preferably 2 m to 2 m + 2, and further preferably 2 m + 1 to 2 m + 2.

X represents the average molecular weight and molecular weight distribution of Compound A by high performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC-MS), and by measuring n ₁ and m by GPC, Can be calculated.

In the compound A, when R includes the group 1 or the group 2, the ratio of the average number y of the total of the glycidyl group and the methyl glycidyl group and the average number z of the total of the group 1 and the group 2 (Y / z) is 10/90 to 90/10, preferably 20/80 to 80/20, more preferably 30/70 to 70/30, still more preferably 40/60 to 60/40. .

In the compound A, from the viewpoint of strong adhesion, each R is independently a hydrogen atom, glycidyl group, methyl glycidyl group, group 1 or group 2, and preferably a hydrogen atom, glycidyl group or group 1. R 'is preferably a hydrogen atom.

When using compound A for the liquid crystal sealant, the viscosity of compound A is preferably 1000 to 1000000 mPa · s, more preferably 3000 to 700000 mPa · s, and still more preferably, from the viewpoint of securing an appropriate viscosity for the liquid crystal sealant. It is 5000 to 500000 mPa · s, more preferably 7000 to 250,000 mPa · s, and further preferably 9000 to 200000 mPa · s. The viscosity is measured at 25 ° C. using an E-type viscometer.

The viscosity of compound A can be adjusted, for example, by changing n ₁ and m in compound A and / or changing the abundance ratio of hydroxyl groups in compound A.

When Compound A is used for the liquid crystal sealant, the epoxy equivalent is preferably 100 to 3000 g / eq, more preferably 150 to 2000 g / eq from the viewpoint of strong adhesiveness.

The epoxy equivalent of compound A can be adjusted by the average molecular weight of compound A and the number of epoxy groups per repeating unit. For example, it can be adjusted by the ratio of epoxidizing the hydroxyl group of compound P and by the ratio of (meth) acrylate modification of the epoxy group of reactant Q.

Compound A is a liquid crystal dropping method, and even when it comes into contact with the liquid crystal in an uncured state, it hardly affects the alignment of the liquid crystal (change in the NI point is small) and does not easily disturb the alignment of the liquid crystal. Preferred as an agent.

[Liquid crystal sealant containing compound A]
A liquid crystal sealant containing compound A (hereinafter also referred to as “composition”) is excellent in strong adhesion.

From the viewpoint of strong adhesion and liquid crystal orientation, the content of compound A is preferably 10 to 10 in the reactive curable component of the liquid crystal sealant (for example, a component that can be cured by reaction with light and / or heating). 100% by weight, more preferably 20 to 100% by weight, still more preferably 30 to 100% by weight, still more preferably 40 to 100% by weight, still more preferably 50 to 100% by weight, More preferred is 60 to 100% by weight, still more preferred is 70 to 100% by weight, still more preferred is 80 to 100% by weight, still more preferred is 90 to 100% by weight, still more preferred is 100% by weight. It is.

For example, Compound A together with Compound B having a conventional ethylenically unsaturated group and / or epoxy group (for example, an oligomer in which a part of epoxy group of bisphenol A type epoxy resin is methacrylated) used as a main component of liquid crystal sealant Compared with the case of compound B alone, the liquid crystal sealant containing the compound significantly improves the strong adhesiveness. That is, the liquid crystal sealant preferably contains, in addition to compound A, compound B having an ethylenically unsaturated group and / or an epoxy group other than compound A.

Examples of the compound B 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 (meth) acrylate compounds include fats represented by paracumylphenoxyethylene glycol (meth) acrylate, t-butyl (meth) acrylate, ethoxylated phenyl (meth) acrylate, benzyl (meth) acrylate, and glycidyl (meth) acrylate. Group (meth) acrylate, aromatic ring-containing (meth) acrylate.

Examples of the ethylenically unsaturated group-containing compound include monofunctional, difunctional, trifunctional or polyfunctional radically polymerizable unsaturated compounds.

Monofunctional radically polymerizable unsaturated compounds include hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and isooctyl from the viewpoint of ensuring composition viscosity, film hardness, and flexibility. (Meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclohexyloxyethyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isomyristyl (meth) One or more compounds selected from the group consisting of acrylate, lauryl (meth) acrylate, tert-butyl (meth) acrylate and diethylene glycol monoethyl ether (meth) acrylate are preferred, Runiru (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, one or more compounds selected from the group consisting of dicyclopentanyl (meth) acrylate and cyclohexyl (meth) acrylate are more preferred.

As a bifunctional radically polymerizable unsaturated compound, from the viewpoint of ensuring composition viscosity, film hardness, and flexibility, tricyclodecane dimethanol di (meth) acrylate, dimethylol dicyclopentanedi (meth) 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, polyethylene glycol di (meth) acrylate, silicone One or more compounds selected from the group consisting of di (meth) acrylate and triethylene glycol di (meth) acrylate are preferred, and dimethylol dicyclopentane di (meth) acrylate and / or modified bisphenol A di (meth) acrylate is preferably used. Yo Preferred. Among them, (meth) acrylates having no hydroxyl group and having a bisphenol A skeleton are preferable. From Kyoeisha Chemical Co., Ltd., light acrylate BP-4EAL (EO addition product of bisphenol A), BP-4PA (PO addition of bisphenol A) Product diacrylate) and the like are commercially available.

Trifunctional or higher radical polymerizable unsaturated compounds include ECH-modified glycerol tri (meth) acrylate (trifunctional) and EO-modified glycerol tri (meth) acrylate from the viewpoint of ensuring composition viscosity, film hardness, and flexibility. (Trifunctional), PO-modified glycerol tri (meth) acrylate (trifunctional), pentaerythritol tri (meth) acrylate (trifunctional), dipentaerythritol hexa (meth) acrylate (hexafunctional) and pentaerythritol tetra (meth) acrylate One or more compounds selected from the group consisting of (tetrafunctional) are preferable, and EO-modified glycerol tri (meth) acrylate and / or dipentaerythritol hexa (meth) acrylate are more preferable.

The compound B 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 novolac type epoxy compound, a naphthalene type epoxy compound, or a hydrogen thereof. It is at least one compound selected from the group consisting of an additive compound and an alicyclic epoxy compound, more preferably at least one selected from the group consisting of a bisphenol A type epoxy compound, a bisphenol F type epoxy compound and a naphthalene type epoxy compound. It is a seed compound, and more preferably a bisphenol A type epoxy compound.

Specific examples of the bisphenol A type epoxy compound include EPICLON 850S, 860, 1055, and EPICLON 850CRP 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 alicyclic epoxy compound include 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate (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).

As the compound B having an ethylenically unsaturated group and an epoxy group, a partial (meth) acrylate-modified epoxy compound obtained by reacting an epoxy group-containing compound with a (meth) acrylic acid compound can also be used. A partial (meth) acrylated epoxy compound obtained by reacting an epoxy compound with (meth) acrylic acid is more preferred.

A partial (meth) acrylated epoxy resin obtained by reacting a bisphenol A type epoxy resin and (meth) acrylic acid is obtained, for example, as follows.
First, bisphenol A type epoxy resin and (meth) acrylic acid are added in the presence of a basic catalyst, preferably in the presence of a trivalent organic phosphoric acid compound and / or an amine compound. ˜90 equivalent% is reacted. Next, the reaction product is purified by removing the basic catalyst by filtration, centrifugation, and / or washing with water. As the basic catalyst, a known basic catalyst used by a reaction between 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.

When the compound A does not contain an ethylenically unsaturated group, the compound B preferably contains a radical curable compound containing an ethylenically unsaturated group-containing compound as a preferred example.

The liquid crystal sealant of the present invention contains a photopolymerization initiator (a compound that is activated by absorbing light energy and generates radicals) as a radical generation source when photopolymerizing compound A and / or compound B. be able to. A polymerization initiator is not specifically limited, A well-known compound can be used as a polymerization initiator. As polymerization initiators, benzoins, acetophenones, benzophenones, thioxanthones, α-acyloxime esters, phenylglyoxylates, benzyls, azo compounds, diphenyl sulfide compounds, acylphosphine oxide compounds, benzoin ethers And anthraquinone polymerization initiators are preferable, and those having a reactive group that has low solubility in liquid crystals and does not gasify the decomposition product itself upon irradiation with light are preferable. As a preferable polymerization initiator of the present invention, for example, the following:

And, for example, EY Resin KR-2 (manufactured by KS Corporation).

As the curing agent, an amine curing agent such as an organic acid dihydrazide compound, imidazole and its derivatives, dicyandiamide, aromatic amine, epoxy-modified polyamine, polyaminourea and the like are preferable from the viewpoint of strong adhesiveness, and organic acid dihydrazide. VDH (1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin), ADH (adipic acid dihydrazide), UDH (7,11-octadecadiene-1,18-dicarbohydrazide) and LDH (octadecane- 1,18-dicarboxylic acid dihydrazide) is preferred. These curing agents may be used alone or in combination.

Examples of the photosensitizer include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes from the viewpoint of curability. Specific examples of photosensitizers include benzoin derivatives such as benzoin methyl ether, benzoin isopropyl ether, α, α-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate. Benzophenone derivatives such as 4,4′-bis (diethylamino) benzophenone; thioxanthone derivatives such as 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone; 2-chloroanthraquinone, 2-methylanthraquinone, etc. Anthraquinone derivatives; acridone derivatives such as N-methylacridone and N-butylacridone; other α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compounds Etc. These photosensitizers may be used alone or in combination of two or more. A preferred photosensitizer is 2,4-diethylthioxanthone (for example, DETX-S manufactured by Nippon Kayaku).

The liquid crystal sealant of the present invention can contain a curing accelerator from the viewpoint of accelerating the curing reaction of the curable compound, and is preferably an imidazo such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole. Tert-amines, 2- (dimethylaminomethyl) phenol and 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU); phosphines such as triphenylphosphine; octylic acid Examples thereof include metal compounds such as tin.

In the liquid crystal sealant of the present invention, a filler can be added from the viewpoints of viscosity control, further improvement in strength after curing, adhesion reliability, and suppression of linear expansion. As the filler, an inorganic filler and an organic filler can be used. As inorganic fillers, 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 silicon nitride Is mentioned. Examples of the organic filler include polymethyl methacrylate, polystyrene, a copolymer obtained by copolymerizing a monomer constituting these and another monomer, polyester fine particles, polyurethane fine particles, and rubber fine particles.

From the viewpoint of further reducing outgassing by adding a filler that is a non-reactive component, the average particle size of the particles constituting the filler is 0.1 to 3 μm, and more preferably 0.5 to 3 μm. The average particle size of the filler is measured by a laser diffraction / scattering particle size distribution measuring device manufactured by HORIBA (for example, Partica LA-950V2 manufactured by HORIBA).

The liquid crystal sealant of the present invention can contain a silane coupling agent within the scope of the effects of the present invention.

From the viewpoint of the stability of the curing strength of the liquid crystal sealant of the present invention, the silane coupling agent is preferably tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethoxydiethoxy. Tetraalkoxysilanes such as silane, dimethoxydiisopropoxysilane, diethoxydiisopropoxysilane, diethoxydibutoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltriethoxysilane, ethyltri Butoxysilane, cyclohexyltriethoxysilane, phenyltriisopropoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyl Trialkoxysilanes such as limethoxysilane; and at least one selected from the group consisting of dialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diethyldibutoxysilane, and phenylethyldiethoxysilane The silane coupling agent is preferably methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltriethoxysilane, ethyltributoxysilane, cyclohexyltriethoxysilane, phenyltriisopropoxysilane, vinyltrimethoxysilane, At least one trialkoxysilane-based sila selected from the group consisting of 3-glycidoxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane Coupling agents are more preferable, 3- glycidoxypropyltrimethoxysilane is more preferable.

[Method for Producing Compound A]
The process for producing compound A of the present invention comprises:
Following formula (2):

(Wherein n ₂ is a number in the range of 2 to 30, Y is independently an alkylene group having 2 to 4 carbon atoms, and R ¹¹ is independently of each other a hydrogen atom, glycidyl Group C or a methyl glycidyl group),
Following formula (3):

[Wherein, X is an oxygen atom (O), an alkylene group having 1 to 4 carbon atoms or an alkylidene group having 2 to 4 carbon atoms, and R ^{12 s} independently of one another are a hydrogen atom, a glycidyl group, Methyl glycidyl group, group 1: —CH ₂ —CH (OR ²¹ ) —CH ₂ —O—R ²² or group 2: —CH ₂ —C (CH ₃ ) (OR ²¹ ) —CH ₂ —O—R ²² ( Wherein R ²¹ is a hydrogen atom or a (meth) acryloyl group, and R ²² is a (meth) acryloyl group)].

N ₂ in Compound C may be selected so that n _{1 of} Compound A falls within the above-mentioned range from the viewpoint of strong adhesiveness of Compound A, and is a number in the range of 3 to 25, preferably 5 to 20 The number is in the range, more preferably in the range of 5 to 15, and still more preferably in the range of 7 to 10. Moreover, the molecular weight (weight average molecular weight) of the compound C in which R ¹¹ is a hydrogen atom is preferably 2000 or less.

Y in the compound C is an alkylene group having 2 to 4 carbon atoms, specifically, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, or the like. Y is preferably an ethylene group or a propylene group, and more preferably an ethylene group.

Compounds C and D are commercially available or can be easily prepared from commercially available compounds according to known methods. For example, as compound C in which R ¹¹ is a hydrogen atom and Y is an ethylene group, those having various numbers of repeating units (n ₂ ) as polyethylene glycol are available, and compounds having a desired range of n ₂ May be appropriately selected. N ₂ can also be calculated in the same manner as n ₁ . The molecular weight of polyethylene glycol is preferably 2000 or less.

Further, as compound C in which R ¹¹ is a hydrogen atom and Y is a propylene group, compounds having various numbers of repeating units 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. The molecular weight of polypropylene ether glycol is preferably 2000 or less.

In addition, compound C in which R ¹¹ is a hydrogen atom and Y is a trimethylene group can be obtained, for example, as polytrimethylene ether glycol having various numbers of repeating units according to the method described in JP2013-515144A. It can be manufactured. The molecular weight of polytrimethylene ether glycol is preferably 2000 or less.

Further, as compound C in which R ¹¹ is a hydrogen atom and Y is a tetramethylene group, those having various numbers of repeating units as polytetramethylene ether glycol are available. For example, PTMG650, PTMG850, PTMG1000, PTMG1300, PTMG1500, PTMG1800, PTMG2000 (above, manufactured by Mitsubishi Chemical Corporation) and the like can be mentioned. The molecular weight of polytetramethylene ether glycol is preferably 2000 or less.

From R ¹¹ in Compound C and R ¹² in Compound D, from the viewpoint of strong adhesion of Compound A, it is preferable that one of R ¹¹ and R ¹² is a hydrogen atom and the other is a glycidyl group.

The compound C and the compound D are produced by, for example, reacting the compound C and the compound D in the presence of an alkali, and then reacting the reaction product of the compound C and the compound D with the presence of an appropriate catalyst. Below, it is made to react with the compound which can introduce | transduce glycidyl groups or methylglycidyl groups, such as epichlorohydrin. The reaction described above is adjusted so that m in compound A is a number in the range of 1 to 5, preferably 1 to 4, more preferably 1 to 3, and more preferably 1 to 2.

The number of m can be controlled as follows when the synthesis intermediate P is synthesized in the case of the example. For example, in Example 1-1, the equivalent ratio of the compounds C1-1 and D1 is 1: 2.5. When this ratio is 1: 2.0 or 1: 1.5, the number of m is Increase. Conversely, even when 1:10, 1: 100, 1: 1000, etc., it is not less than 1. In compound P, m = 0 is such that R of compound D is a hydrogen atom and X is isopropylidene (ie, bisphenol A itself).

From the viewpoint of reactivity, it is preferable that one of R ¹¹ in Compound C and R ¹² in Compound D is a hydrogen atom, and the other is a glycidyl group.

The alkali is preferably an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an alkali metal carbonate such as sodium carbonate or potassium carbonate from the viewpoint of rapid progress of the reaction and synthesis cost. 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.

The amount of alkali used is such that when R ¹¹ is a hydrogen atom and R ¹² is a glycidyl group from the viewpoint of rapid progress of the reaction and synthesis cost, the alkali may be equal to or more than the equivalent of the hydroxyl group, and R ¹¹ is glycidyl. When R ¹² is a hydrogen atom, a catalytic amount is sufficient, and it is 0.0001 to 0.1 equivalent, more preferably 0.0001 to 0.01 equivalent of the hydroxyl group of compound D. For example, in Example 1-1, 1.5 g of 4% sodium hydroxide solution = 0.015 equivalents of sodium hydroxide is used for 2.5 equivalents = 5.0 equivalents of hydroxyl groups of bisphenol A. The amount of alkali used is 0.0003 equivalent to 1 equivalent of hydroxyl group.

The amount of the compound such as epichlorohydrin used is preferably 0.5 to 20 equivalents, more preferably 0.5 to 15 equivalents, from the viewpoint of rapid progress of the reaction and synthesis cost.

Catalysts include tertiary amines such as trimethylamine, trioctylamine and tridecylamine, tetramethylammonium, methyltrioctylammonium, methyltridecylammonium and benzyltrimethylammonium from the viewpoints of reaction time, catalyst cost and catalytic activity. A quaternary ammonium salt such as tetramethylammonium chloride, methyltrioctoctylammonium chloride, methyltridecylammonium chloride, and benzyltrimethylammonium chloride is preferred, and a quaternary ammonium salt is more preferred.

The amount of the catalyst used is preferably 0.01 to 10% by weight with respect to the total amount of compounds such as Compound C, Compound D and epichlorohydrin, from the viewpoint of appropriately securing the reaction rate while suppressing side reactions. %, More preferably 0.1 to 5% by weight.

The reaction with the alkali is preferably performed at 50 to 250 ° C., more preferably at 70 to 200 ° C., and further preferably at 100 to 170 ° C. The reaction with the compound such as epichlorohydrin is preferably The reaction is performed at 25 to 100 ° C, more preferably 30 to 80 ° C, and further preferably 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 excessive amount of a compound such as epichlorohydrin is used, a compound such as epichlorohydrin is used as the solvent. These solvents are not essential.

Purification of compound A after completion of the reaction can be performed by a conventional method, for example, by distilling off an excess of epichlorohydrin and the like, and adding a water-insoluble solvent such as hydrocarbon as necessary, The desired compound A can be obtained by removing the sodium chloride and catalyst produced by washing with water.

From the viewpoint that a general-purpose raw material can be used as the compound C and the compound D, the production method of the compound A of the present invention is a compound C1 (polyalkylene ether glycol diglycidyl ether in which R ¹¹ in the compound C is a glycidyl group; for example, polyethylene glycol Diglycidyl ether), and R ¹² in compound D is a compound D1 (for example, bisphenol A) in which R ¹² is a hydrogen atom, the compound C1 and the compound D1 are reacted to form the compound C1 and the compound D1. It is preferable to include a step 1 for obtaining the reactant P and a step 2 for obtaining a reactant Q in which part or all of the hydroxyl groups of the reactant P are epoxidized by epoxidizing the hydroxyl group of the reactant P.

In this case, compound A in which group 1 or group 2 is introduced into R can be obtained through step 3 in which reactant Q is further reacted with (meth) acrylic acid in the presence of a basic catalyst.

As the basic catalyst, a basic catalyst used by a reaction between an epoxy resin and (meth) acrylic acid can be used from the viewpoint of improving the reaction rate, rapid progress of the reaction, and catalyst cost. It is also possible to use a polymer-supported basic catalyst in which is supported on a polymer. The basic catalyst is preferably a trivalent organic phosphorus compound and / or an amine compound. The basic atom of the basic catalyst is phosphorus and / or nitrogen.

As the basic catalyst, a known basic catalyst used by a reaction between 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. The basic catalyst is preferably a trivalent organic phosphorus compound and / or an amine compound. The basic atom of the basic catalyst is phosphorus and / or nitrogen.

Examples of trivalent organic phosphorus compounds include alkylphosphines such as triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine and salts thereof, 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. 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. Of these, triphenylphosphine is preferable.

Examples of amine compounds 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 and salts thereof. Of 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 and benzyltriethylammonium chloride.

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 the solvent (for example, methyl ethyl ketone, methyl isobutyl ketone, toluene etc.) used for reaction with the epoxy resin obtained by the manufacturing method including the process 1 or processes 1 and 2, and a raw material, a product. Is insoluble.

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. Can produce 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 alone 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 Corporation).

The polymer-supported basic catalyst is used in an amount of 0.5 to 5.0 milliequivalents of the polymer-supported basic catalyst with respect to 1 equivalent of epoxy of the epoxy resin obtained by the production method including Step 1 or 2. Preferably, it is 1.0 to 3.0 milliequivalent. It is preferable from the viewpoint of reaction rate, reaction time, and catalyst cost that the ratio of the polymer-supported basic catalyst is within the above range.

In the production method of the present invention, the temperature in the reaction step of the epoxy resin obtained by the production method including step 1 or steps 1 and 2 and (meth) acrylic acid is preferably 60 to 120 ° C., more preferably 80 to 120 ° C. More preferably, it is 90 to 110 ° C.

In the presence of a catalyst, when the epoxy resin obtained by the production method including step 1 or steps 1 and 2 is reacted with (meth) acrylic acid, the gas phase in the reaction system and on the reaction system in order to prevent gelation It is necessary to maintain an appropriate oxygen concentration. 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.

The reaction between the epoxy resin obtained by the production method including Step 1 or Steps 1 and 2 and (meth) acrylic acid is because the partially esterified epoxy resin obtained by this reaction is cured by active energy rays such as ultraviolet rays. It is desirable to carry out the reaction in a container that shields from ultraviolet rays. In addition, the reaction between the epoxy resin obtained by the production method including Step 1 or Steps 1 and 2 and (meth) acrylic acid is a reflux solvent exhibiting good solvent properties with respect to the epoxy resin in order to prevent gas phase polymerization. Although it may be performed in the presence of the solvent, in this case, since it is necessary to remove the solvent after completion of the reaction, it is preferably performed without a solvent. Examples of the reflux solvent include acetone and methyl ethyl ketone.

In the production method of the present invention, after reacting the epoxy resin obtained by the production method including step 1 or steps 1 and 2 with (meth) acrylic acid, the partially esterified epoxy resin removes the polymer-supported basic catalyst. Can be obtained. As a method for removing the polymer-supported basic catalyst, it is preferable to use filtration or centrifugation.

Examples of the method for filtering the polymer-supported basic catalyst include a method of filtering the polymer-supported basic catalyst using, for example, a nylon mesh NY-10HC (manufactured by Sefar, Switzerland) having an opening of 10 μm.

Examples of the method of centrifuging the polymer-supported basic catalyst include a method of removing the polymer-supported basic catalyst by solid-liquid separation using a centrifuge.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples. Unless otherwise specified, “%” is based on weight.

[Comparative Example 1-2] (Compound B)
340 g of bisphenol A type epoxy resin (EXA850CRP, manufactured by DIC Corporation; also used as the compound of Comparative Example 1-1), 90.4 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.5 g of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) And BHT 100 mg were mixed and stirred at 100 ° C. for 6 hours.
418g of compound B of pale yellow transparent viscous substance was obtained.

[Synthesis Example 1] (Compound C1-1)
200 g (2 equivalents / hydroxyl group) of polyethylene glycol # 200, 1110 g (6 equivalents) of epichlorohydrin, 37.1 g (0.1 equivalents) of benzyltrimethylammonium chloride, mechanical stirrer, thermometer, temperature controller, condenser, Place in a 2 liter three-necked round bottom flask equipped with a Dean-Stark trap and dropping funnel. The mixture was then heated to about 50-55 ° C. with stirring under a high vacuum of 70 torr to vigorously reflux epichlorohydrin. 300 g of 48% solution 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, 1 L of chloroform was added, and the mixture was washed 6 times with 1 L of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 171 g of pale yellow transparent liquid compound C1-1.

[Synthesis Example 2] (Compound C1-2)
222 g of pale yellow transparent liquid compound C1-2 was obtained in the same manner as in Synthesis Example 1, except that polyethylene glycol # 200 was changed to 300 g of polyethylene glycol # 300.

[Synthesis Example 3] (Compound C1-4)
250 g (0.5 eq / hydroxyl) of polyethylene glycol # 1000, 277 g (6 eq) of epichlorohydrin, 9.28 g (0.1 eq) of benzyltrimethylammonium chloride, mechanical stirrer, thermometer, temperature controller, condensation Place in a 1 liter three-necked round bottom flask equipped with a kettle, Dean-Stark trap and dropping funnel. The mixture was then heated to about 50-55 ° C. with stirring under a high vacuum of 70 torr to vigorously reflux epichlorohydrin. 75 g of 48% NaOH solution 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 138 g of white waxy solid compound C1-4.

[Example 1-1] (Compound A-1)
(1) Compound C1-1 (145 g (1 equivalent / epoxy group)) and bisphenol A (Compound D1) (570 g (2.5 equivalents)) are placed in an eggplant type flask so that the liquid temperature becomes 150 ° C. Stir with heating. 4 g NaOH aqueous solution 1.5g was added, and it stirred at 150 degreeC for 2 hours. The solution was cooled to a temperature of 60 ° C. or lower, added with 500 mL of chloroform, washed 6 times with 1 L of 1% NaOH aqueous solution and 3 times with 1 L of water. Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is separated by filtration and the like, and the solvent of the obtained organic phase is distilled off by distillation under reduced pressure, which is a synthetic intermediate as a yellow viscous product 290 g of reaction product P-1 was obtained.

(2) Reactant P-1 (170 g), epichlorohydrin (495 g), and benzyltrimethylammonium chloride (16.5 g) with mechanical stirrer, thermometer, temperature controller, condenser, Dean-Stark trap and The flask was placed in a 2 liter three-necked round bottom flask equipped with a dropping funnel. The mixture was then heated to about 50-55 ° C. with stirring under a high vacuum of 70 torr to vigorously reflux epichlorohydrin. 133 g of 48% NaOH solution 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, 1 L of chloroform was added, and the mixture was washed 6 times with 1 L of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 206 g of pale yellow viscous compound A-1 (reaction product Q-1).

[Example 1-2] (Compound A-2)
(1) Compound C1-2 (230 g (1 equivalent / epoxy group)) and bisphenol A (Compound D1) (570 g (2.5 equivalents)) are placed in an eggplant type flask so that the liquid temperature becomes 150 ° C. Stir with heating. 4 g NaOH aqueous solution 1.5g was added, and it stirred at 150 degreeC for 2 hours. The solution was cooled to a temperature of 60 ° C. or lower, added with 500 mL of chloroform, washed 6 times with 1 L of 1% NaOH aqueous solution and 3 times with 1 L of water. Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is filtered off. 366 g of reaction product P-2 was obtained.

(2) Reactants P-2 (203 g), epichlorohydrin (495 g), and benzyltrimethylammonium chloride (16.5 g) were added to a mechanical stirrer, thermometer, temperature controller, condenser, Dean-Stark trap and The flask was placed in a 2 liter three-necked round bottom flask equipped with a dropping funnel. The mixture was then heated to about 50-55 ° C. with stirring under a high vacuum of 70 torr to vigorously reflux epichlorohydrin. 133 g of 48% NaOH solution 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, 1 L of chloroform was added, and the mixture was washed 6 times with 1 L of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 241 g of pale yellow viscous compound A-2 (reaction product Q-2).

[Example 1-3] (Compound A-3)
(1) Denasel EX-830 (compound C1-3) (268 g (1 equivalent / epoxy group)) and bisphenol A (compound D1) (570 g (2.5 equivalents)) manufactured by Nagase ChemteX Corporation in an eggplant type flask The mixture was heated and stirred so that the liquid temperature became 150 ° C. 4 g NaOH aqueous solution 1.5g was added, and it stirred at 150 degreeC for 2 hours. The solution was cooled to a temperature of 60 ° C. or lower, added with 500 mL of chloroform, washed 6 times with 1 L of 1% NaOH aqueous solution and 3 times with 1 L of water. Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is separated by filtration and the like, and the solvent of the obtained organic phase is distilled off by distillation under reduced pressure, which is a synthetic intermediate as a yellow viscous product 375 g of reaction product P-3 was obtained.

(2) Reactants P-3 (200 g), epichlorohydrin (452 g), and benzyltrimethylammonium chloride (15.1 g) with mechanical stirrer, thermometer, temperature controller, condenser, Dean-Stark trap and The flask was placed in a 2 liter three-necked round bottom flask equipped with a dropping funnel. The mixture was then heated to about 50-55 ° C. with stirring under a high vacuum of 70 torr to vigorously reflux epichlorohydrin. 122 g of 48% NaOH solution 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, 1 L of chloroform was added, and the mixture was washed 6 times with 1 L of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 228 g of pale yellow viscous compound A-3 (reaction product Q-3).

[Example 1-4] (Compound A-4)
(1) Compound C1-4 (130 g (0.23 equivalents / epoxy group)) and bisphenol A (Compound D1) (131 g (2.5 equivalents)) are placed in an eggplant type 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 2 hours. The solution was cooled to a temperature of 60 ° C. or lower, added with 500 mL of chloroform, washed 6 times with 1 L of 1% NaOH aqueous solution and 3 times with 1 L of water. Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is separated by filtration and the like, and the solvent of the obtained organic phase is distilled off by distillation under reduced pressure, which is a synthetic intermediate as a yellow viscous product 154 g of reactant P-4 was obtained.

(2) Reactant P-4 (140 g), epichlorohydrin (207 g), and benzyltrimethylammonium chloride (6.94 g) with mechanical stirrer, thermometer, temperature controller, condenser, Dean-Stark trap and The flask was placed in a 2 liter three-necked round bottom flask equipped with a dropping funnel. The mixture was then heated to about 50-55 ° C. with stirring under a high vacuum of 70 torr to vigorously reflux epichlorohydrin. 56 g of 48% NaOH solution 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, 1 L of chloroform was added, and the mixture was washed 6 times with 1 L of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 142 g of pale yellow viscous compound A-4 (reaction product Q-4).

[Example 1-5] (Compound A-5)
A mixture of 320 g of compound A-3 (reactant Q-3), 43.05 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.25 g of triphenylphosphine (basic catalyst, produced by Tokyo Chemical Industry Co., Ltd.), and 50 mg of BHT was mixed at 100 ° C. For 8 hours. 357 g of light yellow viscous compound A-5 was obtained.

[Examples 2-1 to 9 and Comparative Example 2-1]
Each of Compound A-1 to 5 (Examples 1-1 to 5) and Compound B (Comparative Example 1-2), EY Resin KR-2 (manufactured by QSM), Zefaak F351 (manufactured by Gantz Kasei), Seahoster KE-C50HG (manufactured by Nippon Shokubai Co., Ltd.), KBM-403 (silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.), and Amicure VDH (1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, Ajinomoto Fine Techno Were mixed in the blending amounts (parts by weight) shown in Table 1, and then sufficiently kneaded using a three-roll mill (C-43 / 4 × 10 manufactured by Inoue Seisakusho). Examples 2-1 to 9-9 The liquid crystal sealant of Comparative Example 2-1 was obtained.

[Test conditions]
For each of Compounds A-1 to 5 (Examples 1-1 to 5), EPICRON850CRP (Comparative Example 1-1) and Compound B (Comparative Example 1-2), the viscosity and epoxy equivalent were measured, and the orientation was evaluated. Then, the NI point change was measured, the adhesive strength was evaluated for each of the liquid crystal sealants of Examples 2-1 to 9 and Comparative example 2-1 to 3, and the NI point change was measured.

(1) Viscosity measurement The viscosity was measured at 25 ° C. using an E-type viscometer (RE105U manufactured by Toki Sangyo Co., Ltd.).
The rotor and the number of rotations were selected as follows.
Compound A-1: 3 ° × R7.7 rotor, 5 rpm
Compound A-2: 3 ° × R7.7 rotor, rotation speed 10 rpm
Compound A-3: 3 ° × R14 rotor, rotation speed 5 rpm
Compound A-4: 3 ° × R14 rotor, rotation speed 20 rpm
Compound A-5: 3 ° × R7.7 rotor, 5 rpm
EPICLON850CRP: 3 ° x R14 rotor, rotation speed 20rpm
Compound B: 3 ° × R7.7 rotor, rotation speed 10 rpm

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

(3) NI Point Change Measurement Compounds A-1 to 5 (Examples 1-1 to 5), EPICRON 850CRP (Comparative Example 1-1), Compound B (Comparative Example 1-2), and Examples 2-1 to 9 0.1 g of each of the liquid crystal sealant and the liquid crystal sealants of Comparative Examples 2-1 to 3 was placed in an ampoule bottle, and 1 g of liquid crystal (MLC-11900-080, manufactured by Merck & Co.) 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 is measured using a differential scanning calorimeter (DSC, manufactured by PerkinElmer, Inc., PYRIS6), 10 mg of a liquid crystal sample for evaluation is enclosed in an aluminum sample pan, and the measurement is performed at a temperature rising rate of 5 ° C./min. went. 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 viewpoint of reducing impurities, suppressing elution into the liquid crystal, ensuring stable alignment of the liquid crystal, and improving display characteristics, it is preferable that the NI point change is as small as possible.

(4) Evaluation of orientation Compound A-1 is applied on one surface of an ITO glass substrate (60 mm × 70 mm × 0.7 mmt) with two rubbing-treated alignment films (Sunever SE-7492, manufactured by Nissan Chemical Industries, Ltd.). , Spot-apply and seal so that the diameter after bonding at 15 mm intervals is 2 mm or less, and the other surface is bonded, liquid crystal is injected, and then heat-cured in a hot air oven at 120 ° C. for 1 hour for orientation A panel for sex evaluation was created.
Compound A-1 was replaced with compounds A-2 to 5, EPICLON 850CRP, and compound B, respectively, to prepare a panel for evaluating the orientation.

The rubbing process was performed as follows.
Alignment liquid Sunever SE-7492 (Nissan Chemical Co., Ltd.) was added dropwise (0.3 MPa, 5.3 sec) to an TN6070 base (ITP base manufactured by FPD Solutions) and dried using pure water. A coater reached 5000 rpm in 10 seconds, and was applied uniformly under the condition of keeping for 20 seconds (conditions in which the orientation film thickness was 7000 to 8000 mm). After application, pre-baking (85 ° C., 1 min) on a hot plate and post-baking (230 ° C., 60 min) in an oven were performed. Using a cotton cloth rubbing roll, the substrate was fed at a rotation speed of 500 rpm at a speed of 600 mm / min, and a rubbing treatment was performed with an indentation amount of 0.4 mm. The rubbing direction was defined so that the facing substrate was a twist (cross) of 90 °. The rubbed substrate was immersed in pure water and subjected to ultrasonic cleaning. The glass substrate was dried in an oven at 120 ° C. to obtain a rubbed ITO glass substrate with an alignment film.

About the obtained panel, the alignment state of the liquid crystal in the case of a seal | sticker (point application part) was confirmed. The confirmation was performed with an optical microscope, and the polarizing plate was observed in a crossed Nicol state with a test cell sandwiched between them, and the liquid crystal (hereinafter, blank liquid crystal) in the middle part of the seal and the seal was compared with the liquid crystal state at the time of sealing.
A non-uniform part that is different from the state of the blank liquid crystal found when sealing,
If it is not observed at the time of sealing, or if it is a part of the sealing and less than 50 μm from the sealing,
The case where it is a part at the time of sealing and 50 μm or more from the time of sealing, or the whole circumference at the time of sealing and less than 50 μm from the time of sealing is evaluated as △,
The case of 50 μm or more from the whole circumference at the time of sealing and from the time of sealing was evaluated as x.
In addition, it is thought that said non-uniform | heterogenous part shows that liquid crystal orientation is unsatisfactory.

FIGS. 1 and 2 show the alignment state of the liquid crystal during sealing of compounds A-3 (FIG. 1) and A-5 (FIG. 2). When it is not observed at all, it is a part at the time of sealing and less than 50 μm (◯) from the time of sealing. FIG. 3 shows the alignment state of the liquid crystal when the compound B is sealed, and the non-uniform portion different from the blank liquid crystal state found at the time of sealing is 50 μm or more (×) over the entire periphery of the sealing and from the sealing time. It is.

(5) Evaluation of adhesive strength FIG. 4 shows an outline of the test method.
Each of the liquid crystal sealants of Examples 2-1 to 9 and Comparative Examples 2-1 to 3 is 15 mm × 3 mm, 15 mm × 21 mm on an ITO glass substrate (30 mm × 30 mm × 0.5 mmt) dispersed with a 6 μm spacer. Spot coating was performed so that the diameter of the liquid crystal sealant after bonding to the position was 1.5 to 2.5 mmφ. Thereafter, a glass substrate (23 mm × 23 mm × 0.5 mmt) was bonded, and ultraviolet rays (UV irradiation device: UVX-01224S1, manufactured by USHIO INC., 30 seconds at 100 mW / cm 2/365 nm) were irradiated at an illuminance of 3000 mJ / cm ^2. After that, heat curing was performed in a hot air oven at 120 ° C. for 1 hour to prepare a test piece for evaluating the adhesive strength. Using an autograph AGS-500 manufactured by Shimadzu Corporation, the glass substrate of the test piece was fixed, the ITO glass substrate 15 mm × 25 mm was punched out at a speed of 5 mm / min, and the adhesive strength was evaluated. The evaluation results are shown in Table 1.

The entire disclosure of Japanese Patent Application No. 2012-227417 is incorporated herein by reference.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference, Incorporated herein by reference.

Claims

Following formula (1):

[Wherein n 1 is a number in the range of 2-30, m is a number in the range of 1-5,
X is an oxygen atom, an alkylene group having 1 to 4 carbon atoms, or an alkylidene group having 2 to 4 carbon atoms,
Y is each independently an alkylene group having 2 to 4 carbon atoms,
R is independently of each other a hydrogen atom, a glycidyl group, a methylglycidyl group, a group 1: —CH 2 —CH (OR 1 ) —CH 2 —O—R 2 or a group 2: —CH 2 —C (CH 3 ) (OR 1 ) —CH 2 —O—R 2 (wherein R 1 is a hydrogen atom or a (meth) acryloyl group, and R 2 is a (meth) acryloyl group),
Each R ′, independently of one another, is a hydrogen atom or a methyl group;
In R, the total number x of the total of the glycidyl group, the methyl glycidyl group, the group 1 and the group 2 is 2 or more,
When the R includes the group 1 or the group 2, the ratio of the average number y of the total of the glycidyl group and the methylglycidyl group and the average number z of the total of the group 1 and the group 2 (y / z ) Is 10/90 to 90/10].
A liquid crystal sealant comprising the glycidyl ether compound according to claim 1.
3. The liquid crystal sealant according to claim 2, wherein the content of the glycidyl ether compound in the liquid crystal sealant is 10 to 90% by weight.
The liquid crystal sealant according to claim 2 or 3, wherein the liquid crystal sealant further comprises a compound B having an ethylenically unsaturated group and / or an epoxy group (excluding the glycidyl ether compound).
Following formula (2):

(Where n 2 is a number in the range of 2-30,
Y is each independently an alkylene group having 2 to 4 carbon atoms,
R 11 is each independently a hydrogen atom, a glycidyl group or a methyl glycidyl group)
Following formula (3):

[Wherein X is an oxygen atom, an alkylene group having 1 to 4 carbon atoms, or an alkylidene group having 2 to 4 carbon atoms,
R 12 is independently of each other a hydrogen atom, a glycidyl group, a methyl glycidyl group, a group 1: —CH 2 —CH (OR 21 ) —CH 2 —O—R 22 or a group 2: —CH 2 —C (CH 3 ) (OR 21 ) —CH 2 —O—R 22 (wherein R 21 is a hydrogen atom or a (meth) acryloyl group, and R 22 is a (meth) acryloyl group)]. The manufacturing method of the glycidyl ether type compound represented by Formula (1) of Claim 1 including the process made to react.
When the compound C is the compound C1 in which R 11 is a glycidyl group in the formula (2) and the compound D is the compound D1 in which R 12 is a hydrogen atom in the formula (3), Step 1 of reacting compound C1 and compound D1 to obtain reactant P of compound C1 and compound D1, epoxidizing the hydroxyl group of reactant P, The production method according to claim 5, comprising a step 2 of obtaining a reactant Q that is entirely epoxidized.
Furthermore, the manufacturing method of Claim 6 including the process 3 which makes the said reaction material Q react with (meth) acrylic acid in the presence of a basic catalyst.