JP2015129074A - Composition for reinforcing glass end face, glass plate material, and method of producing glass plate material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for reinforcing a glass end face which has photocurability, is solventless, and gives a cured product capable of sufficiently reinforcing an end face of a glass member, and to provide a glass plate material including a protective layer formed of a cured product obtained by applying the composition to a glass member.SOLUTION: The composition for reinforcing a glass end face contains a thiol compound (a) having two or more groups represented by general formula (1) in the molecule, a polymerizable compound (b) having two or more allyl groups in the molecule, and a photopolymerization initiator (c). [In the formula, Rand Reach independently represent a hydrogen atom, a C1-C10 alkyl group, or a C6-C10 aromatic group, and s represents 0 or an integer of 1-2.]

Description

  The present invention relates to a glass end face reinforcing composition for protecting an end face of a glass member, a glass plate material, and a method for producing a glass plate material.

  In recent years, liquid crystal display panels are often used as display devices for in-vehicle use and portable information devices. A glass substrate is mainly used as the substrate of the liquid crystal display panel. Glass substrates are easy to break. For this reason, conventionally, a protective layer is formed on the entire surface including the end face of the glass substrate or a chemical treatment is performed to prevent the glass substrate from cracking and to be practically used.

  In consideration of productivity, the liquid crystal display panel is subjected to patterning and device mounting for forming a solid circuit on a base material made of a large glass substrate, and then the size of each liquid crystal display panel. It is preferable to manufacture using a method of cutting the base material. However, when a base material made of glass is cut, microcracks (fine irregularities) enter the end surface of the glass substrate, which is a cut surface. For this reason, even if a weak impact is applied to the end face, the glass substrate may be broken starting from the micro cracks on the end face. Therefore, in the glass substrate, it is necessary to form a protective layer not only on the front surface and / or the back surface but also on the end surface.

  Conventionally, as a protective layer of a glass member, there is a layer made of a resin film made of epoxy resin, vinyl chloride resin, polyethylene terephthalate resin, Teflon resin, or the like. When a protective layer made of a resin film is formed on a glass member, it is necessary to bond the resin film on the glass member using an adhesive, and then cut and remove the excess resin film. For this reason, the production efficiency was extremely poor.

  In consideration of productivity, the protective layer of the glass member is preferably formed by a method in which a coating is applied and cured. As a glass protective coating, it is important to have fast curing properties. In consideration of environmental load, the glass protective coating is preferably solvent-free.

  As such a glass protective coating, it is conceivable to use a photocurable resin composition in which an acrylate compound using radical polymerization mainly composed of an unsaturated double bond substance and a photopolymerization initiator are blended. . However, such a photocurable resin composition has a problem that poor polymerization occurs in the presence of air. Moreover, since such a photocurable resin composition is hard and brittle, the effect is insufficient to protect the end face of the glass member.

It is also conceivable to use a thermosetting resin composition containing an epoxy resin and an epoxy curing agent as a glass protective coating. However, since the thermosetting resin composition cannot be used for protecting a glass member that is in close contact with a member having poor heat resistance, there is a limitation in use. Moreover, the thermosetting resin composition which mix | blended the epoxy resin and the epoxy hardening | curing agent also had the subject that control of pot life was difficult.
Therefore, a photocurable resin that can be suitably used as a glass protective coating has been demanded.

  Patent Document 1 describes a resin composition for glass protective coatings comprising a component which essentially comprises a polyurethane-vinyl resin block copolymer, or which comprises the block copolymer and a silane coupling agent. . However, the resin composition contains an organic solvent such as toluene or methyl ethyl ketone. For this reason, the load on the environment and work process is large.

  Patent Document 2 discloses a polyol compound having two or more hydroxyl groups in the molecule, an organic polyisocyanate having two or more isocyanate groups in the molecule, and a compound having a hydroxyl group or amino group and an anionic salt-forming group in the molecule. A glass protective coating composition comprising an aqueous urethane resin composition containing an isocyanate-terminated urethane prepolymer obtained from the above is described. The glass protective coating composition described in Patent Document 2 is composed of a water-based urethane resin composition and is highly safe in terms of working environment in that it does not contain an organic solvent. However, since this glass protective coating composition requires a drying process to remove moisture after application, the equipment costs such as heat source and waste water treatment are high.

Conventionally, a thiolene reaction is well known as a reaction that can be photocured without a solvent. Examples of the photocurable composition using the thiolene reaction include those described in Patent Document 3 and Patent Document 4.
Patent Document 3 describes an ultraviolet curable composition containing allyl group-containing acrylic prepolymer, polythiol and a photopolymerization initiator as essential components. Patent Document 3 describes that the composition is applied to paints and adhesives. However, Patent Document 3 does not mention protection of the glass member.

  Patent Document 4 describes a method for producing laminated optical glass that is cured and bonded using a photocurable composition containing polythiol as an essential component and a compound having two or more allyl groups in one molecule as polyene. Yes. The photocurable composition described in Patent Document 4 is used for adhesion of optical glass. However, Patent Document 4 does not mention protection of the glass member.

JP-A-3-153546 Japanese Patent Laid-Open No. 4-89331 Japanese Patent Laid-Open No. 3-139525 Japanese Patent Publication No.62-9545

However, conventionally, there has been no composition for reinforcing a glass end face that has a photo-curing property and provides a cured product that can sufficiently reinforce the end face of a glass member.
The present invention has been made in view of the above circumstances, and has a photocuring property, and a glass end surface reinforcing composition that can provide a cured product that can sufficiently reinforce the end surface of the glass member without using a solvent. It aims at providing the glass plate material provided with the protective layer which consists of hardened | cured material apply | coated to.

  In order to solve the above-mentioned problems, the present inventors have paid attention to a thiolene reaction that can be photocured without a solvent, and have made extensive studies using various compounds. As a result, the inventors have found that a photocurable resin composition containing a specific thiol compound, a specific polymerizable compound, and a photopolymerization initiator may be used as the photocurable resin composition, and the present invention has been conceived. .

That is, this invention relates to the following photocurable resin compositions.
[1] A thiol compound (a) having two or more groups represented by the following general formula (1) in the molecule, a polymerizable compound (b) having two or more allyl groups in the molecule, and photopolymerization. A glass end face reinforcing composition comprising an initiator (c).

[In formula, R < ¹ > and R < ² > respectively independently represents a hydrogen atom, a C1-C10 alkyl group, or a C6-C10 aromatic group, and s represents 0 or the integer of 1-2. . ]

[2] The glass end face reinforcing composition according to [1], wherein either one or both of R ¹ and R ² is an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms.
[3] The glass end face reinforcing composition according to [1] or [2], wherein the thiol compound (a) is an ester compound of a mercapto-containing carboxylic acid represented by the following general formula (2) and a polyhydric alcohol. object.

[Wherein R ¹ , R ² and s are the same as those in the general formula (1). ]

[4] The polyhydric alcohol may be branched alkylene glycol having 2 to 10 carbon atoms, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, cyclohexanediol, Cyclohexanedimethanol, norbornenedimethanol, 2,2-bis [4- (2-hydroxyethyloxy) phenyl] propane, hydrogenated bisphenol A, 4,4 ′-(9-fluorenylidene) bis (2-phenoxyethanol), and The composition for reinforcing a glass end surface according to [3], which is a kind selected from the group consisting of tris (2-hydroxyethyl) isocyanurate.

[5] The glass end face reinforcing composition according to any one of [1] to [4], wherein at least one of the polymerizable compounds (b) is a monomer (b-1) having a molecular weight of less than 500.
[6] The composition for reinforcing a glass end surface according to [5], wherein the monomer (b-1) contains a compound having 2 to 4 allyl groups in the molecule.

[7] The glass end face reinforcing composition according to any one of [1] to [4], wherein at least one of the polymerizable compounds (b) includes an oligomer (b-2) having a molecular weight of 500 to 20000.
[8] The composition for reinforcing a glass end surface according to [7], wherein the oligomer (b-2) contains a compound having 2 to 4 allyl groups in the molecule.

[9] The composition for reinforcing a glass end surface according to [7], wherein the oligomer (b-2) includes one or more compounds represented by the following general formulas (3), (4), and (5).

[Wherein, c is an integer of 1 to 5, R ³ is an alkylene group having 1 to 10 carbon atoms which may have an alkyl group having 1 to 5 carbon atoms as a substituent, and X is 1 carbon atom] A phenylene group or a cyclohexylene group optionally having an alkyl group of -4 as a substituent, and n is an integer of 0-20]

[Wherein c is the same as in the general formula (3), R ⁴ is an alkyl group having 1 to ⁴ carbon atoms or a group represented by the following formula (4 ′), and X is the general formula (3) ) And m is an integer from 3 to 70]

 [Wherein c and X are the same as those in the general formula (4). ]

Wherein, c and X are the same as in the general formula (3), R ³ is the same as each R ³ independently in the general formula (3), p is an integer of from 1 to 10, q Is an integer from 5 to 50. ]

[10] The polymerizable compound (b) according to any one of [7] to [9], including a monomer (b-1) having a molecular weight of less than 500 and an oligomer (b-2) having a molecular weight of 500 to 20000. Composition for reinforcing glass end face.
[11] The number of mercapto groups of the thiol compound (a) is 20 to 220 with respect to 100 terminal ethylenically unsaturated groups of the polymerizable compound (b). Composition for reinforcing glass end face.
[12] The composition for reinforcing a glass end surface according to any one of [1] to [11], wherein the content of the organic solvent is 1% by mass or less.
[13] The glass end face reinforcing composition according to any one of [1] to [12], further including a coloring material.

[14] A glass plate material in which a protective layer made of a cured product of the glass end surface reinforcing composition according to any one of [1] to [13] is formed on an end surface of the glass member.
[15] The method for producing a glass plate material according to [14], wherein the glass base material is cut into a glass member, and an end face of the glass member is any one of [1] to [13]. And a step of forming a protective layer by curing after applying the glass-end-face reinforcing composition described above.

  ADVANTAGE OF THE INVENTION According to this invention, the composition for glass end surface reinforcement which can obtain the hardened | cured material which has photocurability and can fully reinforce the end surface of a glass member without a solvent is realizable. The glass end surface reinforcing composition of the present invention can form a protective layer made of a cured product, for example, by applying it to a glass member and photocuring it. Therefore, a protective layer can be formed on the end surface of the glass member efficiently and easily. For this reason, for example, when the glass member is a glass substrate of a liquid crystal display panel, productivity in the step of forming a protective layer on the end surface of the glass substrate can be improved.

  In the glass plate material of the present invention, a protective layer made of a cured product of the glass end surface reinforcing composition of the present invention is formed on at least the end surface of the glass member. The cured product of the glass end surface reinforcing composition of the present invention has high hardness and excellent adhesion to the glass end surface, and can effectively reinforce the glass end surface. Therefore, the glass plate material of the present invention is difficult to break.

[Glass end face reinforcing composition]
The glass end face reinforcing composition of the present invention is applied to the glass end face and cured to form a cured product, thereby filling the microcracks existing on the glass end face to protect the glass end face and strengthen the glass end face. is there. Therefore, the hardened | cured material of the composition for glass end surface reinforcement of this invention can be used suitably as a protective layer of a glass end surface. Moreover, the composition for reinforcing a glass end surface of the present invention has an excellent adhesive force that can be favorably bonded to a very small portion of an area called a glass end surface. Therefore, the glass end face reinforcing composition of the present invention is particularly favorable as a material for reinforcing the glass end face.

  In the present invention, the glass end surface may be polished or may not be polished. When forming the protective layer which consists of a hardened | cured material of the composition for glass end surface reinforcement on a glass end surface, the direction which formed the protective layer on the glass end surface which is not grind | polished exhibits a remarkable effect.

  In the present invention, the “glass end surface” means a cut surface obtained by cutting glass with a diamond cutter, a laser cutter or the like. Since the glass end face has fine scratches and irregularities (microcracks) that have entered during cutting, it is easy to crack even with a slight impact.

  The composition for reinforcing a glass end surface of the present invention comprises a thiol compound (a) having two or more groups represented by the following general formula (1) in the molecule and a polymerizability having two or more allyl groups in the molecule. It contains a compound (b) and a photopolymerization initiator (c).

<Thiol compound (a)>
In the present invention, the thiol compound (a) has two or more groups represented by the following general formula (1) in the molecule.

In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 10 carbon atoms, and s is an integer of 0 to 2. Represents.
From the viewpoint of improving the strength of the film (cured product) obtained by the curing reaction, the thiol compound (a) preferably has 2 to 4 groups represented by the general formula (1), and has 4 groups. More preferred.

In the general formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 10 carbon atoms. Among them, R ¹ and R ² are each independently preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and still more preferably an alkyl group having 1 to 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-hexyl group, and an n-octyl group. Of these, a methyl group or an ethyl group is preferable.

From the viewpoint of photocurability and storage stability, either one or both of R ¹ and R ² is an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms (that is, secondary or 3). It is preferably a secondary thiol. In particular, it is more preferable that any ^one of R ¹ and R ² is an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms, and the other is a hydrogen atom (that is, a secondary thiol). . That is, the thiol compound (a) is preferably a secondary or tertiary thiol, and more preferably a secondary thiol.

  Specific examples of the thiol compound (a) include phthalic acid di (1-mercaptoethyl ester), phthalic acid di (2-mercaptopropyl ester), phthalic acid di (3-mercaptobutyl ester), phthalic acid di (3- Mercaptoisobutyl ester), ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol Bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakisthiopropionate, dipentaerythritol Xakis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), butanediol bis (2- Mercaptopropionate), octanediol bis (2-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate), dipentaerythritol hexakis (2 -Mercaptopropionate), ethylene glycol bis (3-mercaptoisobutyrate), propylene glycol bis (3-mercaptoisobutyrate), diethylene glycol bis (3-mercaptoiso) Butyrate), butanediol bis (3-mercaptoisobutyrate), octanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptoisobutyrate) ), Dipentaerythritol hexakis (3-mercaptoisobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), propylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate) , Butanediol bis (2-mercaptoisobutyrate), octanediol bis (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol Tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexakis (2-mercaptoisobutyrate), ethylene glycol bis (4-mercaptovalerate), propylene glycol bis (4-mercaptoisovalerate), diethylene glycol bis ( 4-mercaptovalerate), butanediol bis (4-mercaptovalerate), octanediol bis (4-mercaptovalerate), trimethylolpropane tris (4-mercaptovalerate), pentaerythritol tetrakis (4-mercaptovalerate) ), Dipentaerythritol hexakis (4-mercaptovalerate), ethylene glycol bis (3-mercaptovalerate), propylene glycol bis (3-mercaptovalerate), di Tylene glycol bis (3-mercaptovalerate), butanediol bis (3-mercaptovalerate), octanediol bis (3-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), pentaerythritol tetrakis (3 -Mercaptovalerate), dipentaerythritol hexakis (3-mercaptovalerate), hydrogenated bisphenol A bis (3-mercaptobutyrate), bisphenol A dihydroxyethyl ether-3-mercaptobutyrate, 4,4 '-( 9-fluorenylidene) bis (2-phenoxyethyl (3-mercaptobutyrate)), ethylene glycol bis (3-mercapto-3-phenylpropionate), propylene glycol bis (3-mercapto-3-fe Nylpropionate), diethylene glycol bis (3-mercapto-3-phenylpropionate), butanediol bis (3-mercapto-3-phenylpropionate), octanediol bis (3-mercapto-3-phenylpropionate), Trimethylolpropane tris (3-mercapto-3-phenylpropionate), tris-2- (3-mercapto-3-phenylpropionate) ethyl isocyanurate, pentaerythritol tetrakis (3-mercapto-3-phenylpropionate), Dipentaerythritol hexakis (3-mercapto-3-phenylpropionate), 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione And the like.

  The thiol compound (a) is preferably an ester compound of a mercapto group-containing carboxylic acid represented by the following general formula (2) and a polyhydric alcohol.

In the general formula (2), the meanings and preferred ranges of R ¹ , R ² and s are the same as those described in the general formula (1).

  Specific examples of the mercapto group-containing carboxylic acid represented by the general formula (2) include 2-mercaptopropionic acid, 3-mercaptobutyric acid, 2-mercaptoisobutyric acid, 3-mercaptoisobutyric acid, 3-mercaptopropionic acid, 3 -Mercapto-3-phenylpropionic acid, 3-mercapto-3-methylbutyric acid and the like.

The polyhydric alcohol is preferably a compound having 2 to 4 hydroxyl groups in the molecule, and more preferably a compound having 4 hydroxyl groups.
Specific examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 1,4-pentanediol, 1 , 5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, tricyclodecane dimethanol, (2,2-bis (2-hydroxyethoxyphenyl) propane), bisphenol A alkylene Xoxide adduct, bisphenol F alkylene oxide adduct, bisphenol S alkylene oxide adduct, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-hexanediol, 1,3-hexanediol, 2,3 -Hexanediol, 1,4-hexanediol, 2,4-hexanediol, 3,4-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 9,9- Divalent alcohols such as bis [4- (2-hydroxyethyl) phenyl] fluorene; glycerin, diglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tris (2-hydroxyethyl) isocyanurate, hexanetriol, Sorbitol, Pentaerythritol, dipentaerythritol, sucrose, 2,2-bis (2,3-dihydroxy propyloxy phenyl) trivalent or more alcohols such as propane, but the invention is not limited thereto.

  Among them, as the polyhydric alcohol, alkylene glycol having 2 to 10 carbon atoms which may be branched, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, cyclohexanediol, cyclohexane Dimethanol, norbornene dimethanol, 2,2-bis [4- (2-hydroxyethyloxy) phenyl] propane, hydrogenated bisphenol A, 4,4 ′-(9-fluorenylidene) bis (2-phenoxyethanol), and tris It is preferable that it is 1 type chosen from the group which consists of-(2-hydroxyethyl) isocyanurate.

  Polyhydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,2-bis (2,3-dihydroxypropyloxyphenyl) propane, glycerin, Dipentaerythritol, trimethylolethane, trimethylolpropane, pentaerythritol, and tris (2-hydroxyethyl) isocyanurate are preferable in terms of easy availability of raw materials, and trimethylolpropane, pentaerythritol, tris (2- Hydroxyethyl) isocyanurate is more preferable in terms of the number of functional groups and vapor pressure. Each of these can be used alone or in combination of two or more at any ratio.

  In the present invention, the thiol compound (a) may be used alone or in combination of two or more.

<Polymerizable compound (b)>
In the glass end face reinforcing composition of the present invention, a compound having two or more allyl groups in the molecule is used as the polymerizable compound (b). Moreover, in addition to an allyl group, you may have a terminal ethylenically unsaturated group simultaneously. Thereby, by curing the glass end face reinforcing composition, a two-dimensional or three-dimensional network structure is formed, and a cured product having excellent strength can be obtained.

  Examples of conventional photocurable resin compositions include those using a polymerizable compound having a (meth) acryloyl group. However, a compound containing a (meth) acryloyl group tends to be more reactive than a compound containing an allyl group. For this reason, when a compound containing a (meth) acryloyl group is allowed to react with the thiol compound (a), the homopolymerization of the (meth) acryloyl group proceeds at the same time. It may get worse. In addition, acryloyl group homopolymers have almost no adhesion to glass, so that it is difficult to reinforce the glass itself. Therefore, as the group possessed by the polymerizable compound (b), an allyl group is preferable to a (meth) acryloyl group.

  The polymerizable compound (b) having two or more allyl groups in the molecule includes a monomer (b-1) having a molecular weight of less than 500, an oligomer (b-2) having a molecular weight of 500 to 20000, and a polymer having a molecular weight of more than 20000 ( It is possible to include one or more selected from b-3).

In addition, in this application, molecular weight refers to the number average molecular weight of polystyrene conversion measured by GPC (Gel Permeation Chromatography) method on the following conditions.
The measurement conditions of the GPC method are as follows.
Model used: Showa Denko GPC system SIC-480II
Column: Showa Denko GPC columns K-801, K-802, K-802.5
Detector: Showa Denko Co., Ltd. RI-201H
Eluent: Chloroform measurement method: 100 μL of a sample dissolved in chloroform was introduced into a column controlled at 40 ° C., and the molecular weight in terms of polystyrene was measured.

<Monomer (b-1)>
When the polymerizable compound (b) includes a monomer (b-1) having a molecular weight of less than 500, the molecular weight of the monomer (b-1) is preferably less than 350.
The monomer (b-1) preferably contains a compound having 2 to 4 allyl groups in the molecule, and more preferably contains a compound having 3 allyl groups in the molecule.

Specific examples of the monomer (b-1) include triallyl cyanurate, triallyl isocyanurate, diallyl terephthalate, diallyl phthalate, diallyl isophthalate, trimethylolpropane triacrylate, ethylene glycol bisallyl carbonate, diallyl naphthalate, Pentaerythritol diallyl ether, bisphenol A diallyl ether, bisphenol F diallyl ether, propylene glycol diallyl ether, glyceryl diallyl ether, triallyl trimellitate, fluorinated triallyl isocyanurate, CH ₂ ═CH (CF ₂ ) _n CH═CH ₂ Fluorine-containing polyfunctional olefin compounds such as bisolefin represented by (n = 2 to 6), tetraallyloxyethane, allylated cellulose, tetra Rirokishietan, diallyl terephthalate, include diallyl hydrogenated terephthalic acid or the like, it is preferable to use one or more selected from these.

<Oligomer (b-2)>
When the polymerizable compound (b) includes an oligomer (b-2) having a molecular weight of 500 to 20000, the molecular weight of the oligomer (b-2) is preferably 750 to 15000, and more preferably 1000 to 15000. .
The oligomer (b-2) preferably contains a compound having 2 to 4 allyl groups in the molecule, and more preferably contains a compound having two allyl groups in the molecule.

The oligomer (b-2) is a reaction product (particularly an esterification reaction product) of a compound having an alicyclic or aromatic ring and two or more terminal ethylenically unsaturated groups in the molecule and a polyhydric alcohol. It is preferable to include.
Specific examples of the compound having an alicyclic ring or aromatic ring in the molecule and two or more terminal ethylenically unsaturated groups include diallyl benzenedicarboxylate, diallylcyclohexanedicarboxylate, terephthalic acid, or 1,4-cyclohexanedicarboxylic acid. Diallyl and the like.

  A polyhydric alcohol refers to the compound which has a 2 or more hydroxyl group in a molecule | numerator. As the polyhydric alcohol, it is preferable to use a compound having 2 to 4 hydroxyl groups in the molecule. Specific examples include dihydric and tetrahydric alcohols such as ethanediol, propanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaerythritol, trimethylolpropane, and trimethylolethane.

  Specific examples of the oligomer (b-2) include those containing any one or more compounds represented by the following general formulas (3) to (5).

In the above general formula (3), c is an integer of 1 to 5, more preferably 1 to 3, and most preferably 1, that is, a case where the end of the oligomer is an allyl group.
R ³ may have an alkyl group having 1 to 5 carbon atoms (preferably 1 to 3 and more preferably 1) as a substituent, and 1 to 10 carbon atoms (preferably 1 to 5, more preferably 2 to 3 carbon atoms). ) Alkylene group.

In the above general formula (3), X is a phenylene group or cyclohexylene group which may have an alkyl group having 1 to 4 carbon atoms as a substituent, preferably a phenylene group or cyclohexylene having no substituent. It is a group.
Specific examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, and tert-butyl group.
The position at which the phenylene group or cyclohexylene group is bonded to the adjacent carbonyl carbon may be any of the 1,2-position, 1,3-position, and 1,4-position, but the 1,4-position is preferred.
n is an integer of 0 to 20, preferably 0 to 18, and more preferably 0 to 15.

In the general formula (4), c is the same as that in the general formula (3), R ⁴ is an alkyl group having 1 to ⁴ carbon atoms (specific examples are specific examples of the substituent in X of the general formula (3)). And the group represented by the following formula (4 ′). X is the same as in the general formula (3). m is an integer of 3 to 70, preferably 4 to 60, and more preferably 4 to 50.

In the general formula (4 ′), c and X are the same as those in the general formula (4).
The molecular weight of the compound represented by the general formula (4) is preferably 500 to 20,000, more preferably 800 to 18,000, and most preferably 1000 to 16,000.

In the general formula (5), c and X are the same as in the general formula (3), R ³ is the same as R ³ each independently the general formula (3). p is an integer of 1 to 10, preferably 1 to 9, and more preferably 1 to 8. q is an integer of 5 to 50, preferably 5 to 45, and more preferably 5 to 40.
The molecular weight of the compound represented by the general formula (5) is preferably 500 to 20,000, more preferably 500 to 19,000, and most preferably 800 to 18,000.

  Specific examples of the other oligomer (b-2) include trimethylolpropane EO (ethylene oxide) modified triacrylate, tripropylene glycol diacrylate, bisphenol A type EO modified diacrylate, substituted or unsubstituted allyl alcohol. Examples include derived polyene compounds and polyethylene glycol bisallyl carbonate.

<Polymer (b-3)>
When the polymerizable compound (b) includes a polymer (b-3) having a molecular weight of more than 20,000, for example, a polymer (b-3) having two or more allyl groups introduced into the polymer skeleton can be used.
Examples of the polymer skeleton of the polymer (b-3) include a polyethylene skeleton, a polyurethane skeleton, a polyester skeleton, a polyamide skeleton, a polyimide skeleton, a polyoxyalkylene skeleton, and a polyphenylene skeleton.

<When monomer (b-1) and oligomer (b-2) are included>
The polymerizable compound (b) may include a monomer (b-1) having a molecular weight of less than 500 and an oligomer (b-2) having a molecular weight of 500 to 20000. By using such a polymerizable compound (b), the reinforcing effect of the glass end face in the cured product of the glass end face reinforcing composition can be further enhanced. This is because when the glass end face reinforcing composition is cured, the monomer (b-1) has a higher degree of freedom than the oligomer (b-2), so that the crosslinking density increases and the elastic modulus becomes higher. It is estimated to be.

A preferable blending ratio of the monomer (b-1) and the oligomer (b-2) is preferably monomer / oligomer = 10 to 70/90 to 30 by mass ratio, more preferably 30 to 70/70 to 30. It is.
In addition, even if the polymerizable compound (b) is the monomer (b-1) alone or the oligomer (b-2) alone, the curing with excellent adhesion to the glass member and the reinforcing effect of the glass end face. Can form things.

<Ratio of functional groups of thiol compound (a) and polymerizable compound (b)>
The optimum blending amount of the thiol compound (a) and the polymerizable compound (b) is the number of terminal ethylenically unsaturated groups (—CH ₂ ═CH ₃ ) of the polymerizable compound (b) and the thiol compound (a). It depends on the ratio of the number of mercapto groups (—SH).
The number of mercapto groups (ratio of functional groups) of the thiol compound (a) is preferably 20 to 220, more preferably 60 to 170, with respect to 100 terminal ethylenically unsaturated groups of the polymerizable compound (b). . When said functional group number ratio is 20 or more, the hardened | cured material excellent in the adhesiveness to a glass member and the reinforcement effect of a glass end surface can be formed. Moreover, when said functional group number ratio is 220 or less, the hardened | cured material of the composition for glass end surface reinforcement does not have stickiness on the surface, and there is no possibility of contaminating a peripheral member.

The ratio of the number of mercapto groups of the thiol compound (a) to the number of terminal ethylenically unsaturated groups of the polymerizable compound (b) (functional group number ratio) was determined using the following formula.
Polymerizable compound (b) terminal ethylenically unsaturated group (—CH ₂ ═CH ₃ ) equivalent: A (g / eq (gram equivalent))
Compounding amount of polymerizable compound (b): X (g (mass))
Mercapto group (-SH) equivalent of thiol compound: B (g / eq (gram equivalent))
Compounding amount of thiol compound: Y (g (mass))
Functional group number ratio = 100 × (A × Y) / (B × X)

<Photopolymerization initiator (c)>
The photopolymerization initiator (c) is not particularly limited as long as it is a compound that generates radicals that contribute to the initiation of radical polymerization upon irradiation with light such as near infrared rays, visible rays, and ultraviolet rays.
Specific examples of the photopolymerization initiator include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1,2-hydroxy-2-methyl-1-phenylpropane. -1-one, α-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 2-hydroxy-2-methyl-1- (4-isopropylphenyl) propanone, 2-hydroxy-2- Methyl-1- (4-dodecylphenyl) propanone and 2-hydroxy-2-methyl-1-[(2-hydroxyethoxy) phenyl] propanone, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methyl Benzophenone, 4-methoxybe Zophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, benzophenone tetracarboxylic acid or tetramethyl ester thereof, 4 , 4'-bis (dialkylamino) benzophenones (for example, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (dicyclohexylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4, 4'-bis (dihydroxyethylamino) benzophenone), 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethyl Tilaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, fluorenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2 -(Dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholino-1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin) Isopropyl ether, benzo Isobutyl ether, benzoin phenyl ether, benzyldimethyl ketal), acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3 , 5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi- (2,6-dimethylphenyl) phosphonate, 1- [4- (phenylthio) phenyl -1,2-octanedione-2- (O-benzoyloxime), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyloxime) ), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropanone-1- (O-acetyloxime), 1- [4- (phenylthio) Phenyl] -3-cyclopentylpropane-1,2-dione-2- (O-benzoyloxime) and the like.

  Examples of bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) phenyl phosphite Oxide, (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1 -Chloro-4-propoxythioxanthone and the like.

These photopolymerization initiators can be used alone or in combination of two or more. The photopolymerization initiator used in the present invention is a combination of a photopolymerization initiator having an extinction coefficient of 365 nm of 4 × 10 ² ml / g · cm or more and a photopolymerization initiator that generates active methyl radicals. Is preferred.
Examples of the photopolymerization initiator having an extinction coefficient of 365 nm of 4 × 10 ² ml / g · cm or more include Irgacure 907, Irgacure 369, Irgacure 819, Irgacure 1800, Irgacure 784, and Lucirin TPO (both manufactured by BASF). .
Examples of the photopolymerization initiator that generates an active methyl radical include benzyldimethyl ketal and α-hydroxyacetophenones, and examples thereof include Irgacure 651, Irgacure 184, and Darocur 1173 (manufactured by BASF).

  Furthermore, by incorporating a compound having a strong absorption at 350 nm or more, such as thioxanthone and ketocoumarin, an effective photoinitiating system not only for UV light sources but also for LED light sources that are expected to increase in the future. It becomes possible to design. Examples of such a photosensitizer include 2,4-diethylthioxanthen-9-one.

It is preferable to contain 0.1-10 mass parts with respect to 100 mass parts of polymeric compositions, and, as for the usage-amount of a photoinitiator, More preferably, it is the range of 0.4-5 mass parts.
Here, 100 parts by mass of the polymerizable composition means that the total amount of the thiol compound (a) and the polymerizable compound (b) is 100 parts by mass.
When the usage-amount of a photoinitiator is 0.1 mass part or more with respect to 100 mass parts of polymeric compositions, deep part sclerosis | hardenability is easy to be expressed and it is preferable. Moreover, when the usage-amount of a photoinitiator is 10 mass parts or less with respect to 100 mass parts of polymeric compositions, a photoinitiator does not have a possibility of having a bad influence on the physical property of hardened | cured material, and is preferable.
However, when the polymerizable composition contains a coloring material, it is preferable that the amount of the photopolymerization initiator is large from the viewpoint of promoting deep curing, specifically, with respect to 100 parts by mass of the polymerizable composition, It is preferable that it is 0.1-20 mass parts, and it is more preferable that it is 5-15 mass parts.

  Moreover, a metallocene compound can also be used as a photocuring accelerator. As the metallocene compound, the transition metal represented by Fe, Ti, V, Cr, Mn, Co, Ni, Mo, Ru, Rh, Lu, Ta, W, Os, Ir, etc. can be used as the metallocene compound, An example is bis (η5-2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (pyrrol-1-yl) phenyl] titanium.

<Other ingredients>
The glass end face reinforcing composition of the present invention may further contain a coloring material such as a carbon material, a pigment, or a dye. You may use these individually or in combination of 2 or more types.
In some cases, the end face of the liquid crystal display panel is required not to leak light. For this reason, conventionally, after forming a protective layer for preventing cracks on the end face of the glass substrate of the liquid crystal display panel, a two-stage process of applying a highly light-shielding resin composition on the protective layer is required. There was a case.

  When the glass end surface reinforcing composition of the present invention contains the coloring material, the cured product of the glass end surface reinforcing composition has both a function of protecting the end surface of the glass member and a function of preventing light leakage. . Therefore, when it is required that no light leaks from the end face, a protective layer made of a cured product of the glass end face reinforcing composition containing the coloring material may be formed on the end face of the glass substrate of the liquid crystal display panel. preferable. As a result, the manufacturing process can be simplified and the productivity can be improved.

Examples of the carbon material include carbon black, acetylene black, lamp black, and graphite, and examples thereof include the following commercially available carbon black.
Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA220, MA230, # 52, # 50, # 47, # 45, # 2700, # 2650, 32200, # 1000, # 990, # 900.

  Made by Degussa: Protex95, Printex90, Printex85, Printex75, Printex55, Printex45, Printex40, Printex30, Printex3, Printex A, Printex G, Special 250, 350, Print5, 350, Print5.

  Manufactured by Cabot Corporation: Monarch 460, Monarch 430, Monarch 280, Monarch 120, Monarch 800, Monarch 4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, BLACK PEARL480, PEARL.

  Made by Colombian Carbon: Raven11, Raven15, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven850, Raven1000, Raven1020, Raven1020, Raven1080, Raven1080, Raven1080

Other examples of black pigments include iron black, aniline black, cyanine black, and titanium black.
The following are mentioned as a pigment. Both are indicated by Color Index Constitution Number (color index number: CI).

  Note that the C.I. I. Means “The Society of Dyers and Colorists and The American Association of Textile Chemists and Colorists”. “Number”.

C. I. Pigment Yellow 12, 13, 14, 17, 20, 24, 55, 83, 86, 93, 109, 110, 117, 125, 137, 139, 147, 148, 153, 154, 166, 168.
C. I. Pigment Orange 36, 43, 51, 55, 59, 61.
C. I. Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240.
C. I. Pigment Violet 19, 23, 29, 30, 37, 40, 50.
C. I. Pigment Blue 15, 15: 1, 15: 4, 15: 6, 22, 60, 64.
C. I. Pigment Green 7, 36.
C. I. Pigment Brown 23, 25, 26.
C. I. Pigment Black7.

Examples of the dye include direct dyes, acid dyes, basic dyes, mordant dyes, acid mordant dyes, vat dyes, disperse dyes, reactive dyes, fluorescent whitening dyes, and plastic dyes. It is preferable to use a mixture of two or more dyes in order to impart a light shielding property to visible light in a wide wavelength range.
The dye means a substance that is soluble or compatible with the thiol compound (a) or the polymerizable compound (b) and has a property of coloring the dissolved and / or compatible substance.

  Preferred among these dyes are plastic dyes intended to dye resins. Examples of plastic dyes include monoazo dyes (CI 11000 to 19999), diazo dyes (CI 20000 to 29999), triaryl dyes (CI 42000 to 49999), and quinoline dyes. (CI. 470000-49999), methine dyes (CI. 48000-48999), azine dyes (CI. 50000-50999), aminoketone dyes (CI. 56000-56999), anthraquinones System dyes (C.I. 58000-72699), indigoid dyes (C.I. 72000-72999), and the like.

  The content of the coloring material in the glass end face reinforcing composition is not particularly limited. However, if the concentration of the coloring material is too high, the light transmittance may be lowered to cause curing failure. If the concentration of the coloring material is too low, the light transmittance is increased, and there is a possibility that light leakage from the end face of the glass member cannot be sufficiently prevented. Therefore, it is preferable that content of a coloring material exists in the range of 0.1-40 mass parts with respect to 100 mass parts of polymeric compositions, More preferably, it is 0.15-35 mass parts.

  In addition to the polymerizable compound (b), the glass end face reinforcing composition includes a photocurable monomer, a thermosetting resin, a thermoplastic resin, a deodorant, an antioxidant, an ultraviolet absorber, and a plasticizer. , Waxes, reactive diluents, foaming agents, carbodiimide compounds and other dehydrating agents, antistatic agents, antibacterial agents, fungicides, viscosity modifiers, flame retardants, dispersants, fragrances and the like. These additives may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

Examples of the antioxidant include hindered amines, hydroquinones, hindered phenols and the like.
Examples of the ultraviolet absorber include benzophenones, benzotriazoles, salicylic acid esters, metal complex salts and the like.
Examples of the plasticizer include phthalic acid esters, phosphoric acid esters, and fatty acid esters.
Examples of waxes include paraffin wax, microcrystalline wax, and polymer wax.
Examples of the reactive diluent include low molecular weight aliphatic glycidyl ether and aromatic monoglycidyl ether.

  Furthermore, a polymerization inhibitor may be added to the glass end face reinforcing composition of the present invention for the purpose of improving storage stability. As the polymerization inhibitor, those generally used can be used, and examples thereof include phenols such as hydroquinones, catechols, and resorcins, phenothiazines, and N-nitrosophenylhydroxylamine salts.

<Solvent>
In the composition for reinforcing a glass end surface of the present invention, the content of the organic solvent is preferably 1% by mass or less, more preferably 0.1% by mass or less, and most preferably none. The composition for reinforcing a glass end surface of the present invention has a small amount of organic solvent or does not contain an organic solvent, so that heat shrinkage during curing can be suppressed, and the organic solvent should be avoided. Can be used.
The shrinkage during the curing of the glass end face reinforcing composition is preferably small, and specifically, the curing shrinkage rate is preferably about 10% or less.

Examples of the organic solvent include ethers, esters, ketones, and glycols. A mixture of these may be used as the organic solvent.
Examples of ethers include diisopropyl ether, ethyl isobutyl ether, and butyl ether.

<Preparation method>
The method for preparing the glass end surface reinforcing composition of the present invention is not particularly limited as long as it can mix and disperse the materials used, and examples thereof include the following methods (a) to (g). It is done.
(A) Mixing with a stir bar or spatula in a suitable container such as a glass beaker, a can, or a cup.
(B) Kneading with a double helical ribbon blade, a gate blade or the like.
(C) Kneading with a planetary mixer.
(D) Kneading with a bead mill.
(E) Kneading with three rolls.
(F) Kneading with an extruder type kneading extruder.
(G) Stir using a rotation and revolution type stirrer.

<Application method>
The method for applying the glass end face reinforcing composition of the present invention is not particularly limited, and a conventionally known method can be used. For example, the method of apply | coating with a brush etc. directly to a glass end surface can be used. Moreover, you may use the method of pressing a glass end surface to the composition for glass end surface reinforcement previously apply | coated by the substantially uniform thickness on the film etc., and transferring the composition for glass end surface reinforcement to a glass end surface. Moreover, when applying the glass end surface reinforcing composition to the glass surface, it may be applied using a dispenser or the like.

<Curing method>
A specific method for forming a cured product by photocuring the glass end face reinforcing composition of the present invention is a method using active energy rays. Of the active energy rays, it is economically preferable to use ultraviolet rays or visible rays having a wavelength of 300 to 500 nm. Examples of the active energy ray light source include a mercury lamp, a metal halide lamp, a semiconductor laser, and an LED.

The total exposure amount in photocuring is preferably ¹ to 5 J / cm ² when the coloring material is not contained in the glass end face reinforcing composition. When the coloring material is contained in the glass end face reinforcing composition, the total exposure amount is preferably ¹ to 10 J / cm ² .

  After the glass end face reinforcing composition is cured by the above-described method, it is preferable to anneal the obtained cured product. By this, since the intensity | strength of hardened | cured material improves, a glass end surface can be protected more effectively. In order to obtain the strength improvement effect by performing the annealing treatment, the heating temperature condition is preferably set to 40 ° C. or higher.

<Glass plate material>
In the glass plate material of the present invention, a protective layer made of a cured product of the glass end surface reinforcing composition of the present invention is formed on at least the end surface of the glass member. Since the protective layer has high hardness and excellent adhesion to the glass end surface, the glass end surface can be effectively reinforced. Therefore, the glass plate material of the present invention is difficult to break.

The glass plate material of this invention can be used suitably as a display member of devices, such as a smart phone, for example.
Although it does not specifically limit as a method of mounting the glass plate material of this invention in a device, For example, the following method (1) or (2) etc. are mentioned.
(1) A method of mounting on a device after forming a protective layer on the end face of a glass member.
(2) A method of simultaneously mounting a plurality of device members on a glass base material, then cutting the glass base material into the size of each device to form a glass member, and forming a protective layer on the end face.

  The glass plate material of this invention can be manufactured by the method shown below, for example. First, a glass base material is cut into a glass member. Although it does not specifically limit as a cutting method of a glass base material, For example, a diamond cutter can be used. Further, the glass base material may be cut using a laser cutter. Then, the protective layer is formed by applying and curing the glass end surface reinforcing composition of the present invention on at least the end surface of the glass member. By this, the glass plate material of this invention is obtained.

  Specifically, the glass plate material of the present invention has an evaluation of the following method “reinforcing effect of the glass end face” that is not less than the numerical range shown below. Moreover, the protective layer currently formed in the glass plate material of this invention is evaluation more than the numerical range shown below in evaluation of the method "adhesion evaluation" shown below.

"Reinforcing effect on glass edge"
The reinforcing effect of the glass end face can be evaluated by the following method. First, a sheet glass (glass base material) having a thickness of 0.7 mm or more is broken using a diamond cutter or the like to obtain a glass member. Next, the glass facet reinforcing composition of the present invention is applied to the end face of the glass member to a thickness of 0.1 mm, and after light curing using a UV lamp, annealing treatment is performed to form a protective layer made of a cured product. To do. Thereafter, a falling ball test is performed from a height of 1 m on the end surface of the glass member having the protective film, and a load required for the protective layer to peel from the end surface of the glass member and a load necessary for breaking the glass member are measured.
The thickness of the protective film can be measured by a method of measuring using a surface roughness tester after removing a part of the protective film. Moreover, you may measure the thickness of a protective film by the method of observing the cross section of a protective film using a scanning electron microscope (SEM).

  When the glass plate material of the present invention is evaluated for the reinforcing effect of the glass end face by the above-described method, the protective layer has a load of 1.2 times or less compared to an untreated product (without a protective layer). Is not peeled off and the glass member is not cracked. In the above evaluation, it is preferable that the protective layer is not peeled off and the glass member is not cracked by a load of 1.3 times or less as compared with the untreated.

"Evaluation of adhesion"
Adhesion can be evaluated by the following method. First, a glass end face reinforcing composition is applied to the surface of a sheet glass so as to have a film thickness of 0.1 mm. Then, a protective layer made of a cured product is formed by photocuring using a UV lamp. Thereafter, an evaluation jig of a pull-off adhesion tester (trade name: Elcomometer 106, manufactured by Elcometer) is bonded to the cured product using a commercially available strong adhesive. Subsequently, the evaluation jig is peeled off in the vertical direction by a tester, and the force necessary for peeling the evaluation jig and the peeling mode are observed.

  The peeling mode includes an interface peeling mode that peels off at the interface between the glass and the cured product, a cohesive failure mode in which the cured product breaks, and a substrate destruction mode in which the glass surface itself breaks due to high adhesion between the glass surface and the cured product. . When the curability of the glass end face protective material is inferior, it becomes a cohesive failure mode, which is not preferable. The peeling mode is preferably the interface peeling mode or the substrate breaking mode, but more preferably the substrate breaking mode.

The protective layer formed on the glass plate material of the present invention is such that when the adhesion is evaluated by the above method, the force required for peeling the evaluation jig representing the adhesion strength is 1 MPa or more. is there. As for said evaluation, it is more preferable that the force required for peeling an evaluation jig | tool is 1.5 Mpa or more.
Moreover, since the protective layer currently formed in the glass plate material of this invention is excellent in sclerosis | hardenability, peeling mode becomes an interface peeling mode or a base-material destruction mode.

  The composition for reinforcing a glass end surface of the present invention is suitable as a material for a protective layer formed on the end surface of a glass member, and particularly suitable as a material for a protective layer formed on the end surface of a glass substrate of a liquid crystal display panel. The composition for reinforcing a glass end surface of the present invention can be used not only as a material for a protective layer on the glass end surface but also as a material for a protective layer on the glass surface. Furthermore, the glass end surface reinforcing composition of the present invention can be used for laminated glass adhesives, exterior paints, structural adhesives, elastic adhesives, adhesives, electronic materials, and the like.

EXAMPLES Hereinafter, although this invention is demonstrated based on an Example and a comparative example, this invention is not restrict | limited at all by the following example.
The glass end face reinforcing compositions of Examples and Comparative Examples were produced, and their characteristics were evaluated as follows.

<Examples 1-11, Comparative Examples 1-5>
The components as shown in Table 1 and Table 2 were mixed and dispersed using a planetary stirrer (trade name: Foaming Netaro ARE-250 (manufactured by Sinky)) to obtain a glass end face reinforcing composition. .

The materials used in Examples 1 to 11 and Comparative Examples 1 to 5 are as follows.
<Thiol compound (a)>
PE1: Pentaerythritol tetrakis (3-mercaptobutyrate) manufactured by Showa Denko KK
NR1: manufactured by Showa Denko KK, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione PETP: penta Erythritol tetrakisthiopropionate

<Polymerizable compound (b)>
TAIC: Nippon Kasei Co., Ltd., triallyl isocyanurate (molecular weight 249.3)
DATP: Showa Denko KK, diallyl terephthalate (molecular weight 246.2)
H-DATP: Showa Denko KK, hydrogenated terephthalate (molecular weight 250.2)

En-oligomer A: 300 g of diallyl 1,4-cyclohexanedicarboxylate, 55 g of pentaerythritol (Tokyo Kasei Co., Ltd.) and 0.3 g of dibutyltin oxide were charged into a three-necked flask and heated in an oil bath adjusted to 180 ° C. for ester exchange reaction. went. The reaction was gradually reduced from normal pressure to 1.4 kPa, and the end of the theoretical amount of allyl alcohol distilled. After cooling, the reaction solution was taken out to obtain 285 g of ene oligomer A (molecular weight: about 12000) represented by the following formula (6).

[Wherein m2 is an integer having a distribution between 4 and 50]

En-oligomer B: 300 g of diallyl terephthalate (Tokyo Chemical Industry Co., Ltd.), 43 g of diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 31 g of propylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 0.3 g of dibutyltin oxide (Tokyo Chemical Industry Co., Ltd.) Was placed in a three-necked flask and heated in an oil bath adjusted to 180 ° C. to conduct a transesterification reaction. The reaction was gradually reduced from normal pressure to 1.4 kPa, and the end of the theoretical amount of allyl alcohol distilled. After cooling, the reaction liquid was taken out, and 275 g of En-oligomer B, which is a mixture of two kinds of en-oligomers represented by the following formula (7) and the following formula (8) (molecular weight: about 1000), was obtained.

[Where n1 is an integer having a distribution between 5 and 15]

[Wherein n2 is an integer having a distribution between 5 and 15]

<Photopolymerization initiator (c)>
Darocure 1173: Lecirin TPO manufactured by BASF Japan Ltd .: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide manufactured by BASF Japan Ltd.

<Other ingredients>
A-BPE-10: Shin-Nakamura Chemical Co., Ltd., ethoxylated bisphenol A diacrylate, trade name “NK ester A-BPE-10” (molecular weight 776)
3 MBA: manufactured by Tokyo Chemical Industry Co., Ltd., 3-mercaptobutanoic acid A-DPH: manufactured by Shin-Nakamura Chemical Co., Ltd., dipentaerythritol hexaacrylate CB: manufactured by Clariant, carbon black, trade name “Special Black 4”

About each obtained composition, the following item was evaluated. The results are shown in Table 3.
《Creating reinforced glass (glass plate material)》
A plate-shaped soda glass substrate having a thickness of 1.1 mm was broken with a diamond cutter to obtain a glass member.
On the other hand, two tapes with a thickness of 0.1 mm were pasted on the film at intervals, and a small amount of the glass reinforcing composition was put between them. The composition was made into the state of the coating film of thickness 0.1mm by sliding the glass rod leveled with respect to the film on two tapes.

The cut surface of the glass member was pressed onto the coating film on the film, and the coating film was transferred to the glass end surface. The coating film on the glass end surface thus formed was irradiated with a UV lamp at a total exposure of 1 J / cm ² (however, only Example 10 containing carbon black was 3 J / cm ² ), and the coating film was irradiated with light. It hardened | cured and the protective layer of the glass end surface was formed, and the glass plate material was obtained.

<Reinforcing effect on glass edge>
The glass plate material created above was fixed in a state perpendicular to the ground so that the reinforced end face was parallel to the ground. And the hard ball made from stainless steel (SUS) of various weights was dropped from the height of 1 m to the center part of the protected glass end surface, and the falling ball test was done. And the load which a protective layer peels from the end surface of a glass member, and the load required in order for a glass member to crack or to lack were measured.

Further, as a reference, a falling ball test was performed on the end face of the glass member on which the protective film was not formed in the same manner as the glass member having the protective film, and a load necessary for breaking the glass member was measured. Based on the results, the following evaluation was performed.
A: Peeling of the protective layer and cracking of the glass member do not occur at a load of 1.2 times or less of the reference.
B: Peeling of the protective layer and cracking of the glass member occur at a load of 1.2 times or less of the reference.

<Glass edge adhesion>
Whether or not the protective film can be peeled off by hand from the glass plate material prepared in the above-mentioned "creation of reinforced glass" was evaluated and evaluated.
A: Cannot be peeled off.
B: Can be peeled off.
《Glass plane adhesion》
The glass end face reinforcing composition was applied to the surface of the plate glass so that the film thickness was 0.1 mm, and the total exposure amount was ² J / cm ² with a UV lamp (however, Example 10 containing carbon black was 4 J / Cm ² ), followed by annealing at 100 ° C. for 30 minutes to form a protective layer made of a cured product. Thereafter, an evaluation jig of a pull-off type adhesion tester (trade name: Elcometer 106, manufactured by Elcometer) was bonded to the cured product using a commercially available strong adhesive. Subsequently, the evaluation jig was peeled off in the vertical direction by a tester, and the force (adhesion strength) necessary for peeling the evaluation jig and the following peeling mode were observed.
A: Substrate destruction mode (the glass surface itself breaks and peels off)
B: Interfacial peeling mode (peeling at the interface between glass and cured product)
C: Cohesive failure mode (hardened product breaks and peels off)

Further, the glass edge reinforcing compositions of Examples and Comparative Examples, mercapto group terminal ethylenically unsaturated group of the polymerizable compound (b) thiol compound for (-CH 2 = _{CH 3)} The number 100 (a) (- The ratio of (SH) number (functional group number ratio) was calculated using the above formula. The results are shown in Table 3.
In Tables 1 and 2, “ene equivalent” represents the terminal ethylenically unsaturated group equivalent of the polymerizable compound (b). “SH equivalent” indicates the mercapto group equivalent of the thiol compound.
In Table 3, “(—SH / —CH ₂ ═CH ₃ )” represents the functional group number ratio.

  From Tables 1 to 3, in Examples 1 to 11 containing the thiol compound (a), the polymerizable compound (b), and the photopolymerization initiator (c), the reinforcing effect of the glass end surface and the evaluation of the glass end surface adhesion are evaluated. Were all A. In Examples 1 to 11, the adhesion strength was 1.0 MPa or more, and it was confirmed that the adhesion was excellent.

  On the other hand, Comparative Example 1 containing no thiol compound (a), Comparative Example 2 containing no photopolymerization initiator, and Comparative Example using a compound having only one mercapto group in the molecule as the thiol compound In No. 5, since there was no photopolymerizability and it was not photocured, the evaluation of the adhesion strength and the reinforcing effect was impossible.

In Comparative Example 3 and Comparative Example 4, a compound having an acryloyl group instead of an allyl group was used in place of the polymerizable compound (b). In Comparative Example 3 and Comparative Example 4, the glass end face reinforcing effect and the glass end face adhesion were inferior to the case where the compound having an allyl group was used.
In the adhesion evaluation of Examples 1 to 10, Comparative Example 3 and Comparative Example 4, none of the cohesive failure modes was found.

<Comparative Example 6>
Prepare 100g of jER828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical), 10g of PE1, and 5g of Curazole 2E4MZ (2-ethyl-4-methylimidazole, manufactured by Shikoku Kasei). A glass end face reinforcing composition was obtained by mixing and dispersing using Nertaro ARE-250 (manufactured by Shinky Corporation).
This composition was allowed to stand at room temperature. As a result, when 40 minutes passed from the start of stirring, the temperature suddenly increased and the composition was cured.

On the other hand, in the glass end face reinforcing composition of Example 11, even if the composition was allowed to stand at room temperature for 1 hour or more after the start of stirring of the raw material, the temperature of the composition and curing did not proceed.
From this result, Example 11 which is an enethiol-based curable composition has a longer pot life than Comparative Example 6 which is an epoxythiol-based curable composition, and is suitably used as a glass end face reinforcing composition. I understood that I could do it.

  The glass end face reinforcing composition of the present invention has photocurability, is solventless, and has little environmental load. And the composition for glass end surface reinforcement of this invention can obtain the hardened | cured material which can fully reinforce the end surface of a glass member. For this reason, for example, the glass end face reinforcing composition of the present invention is applied to the end face of the glass substrate of the liquid crystal display panel and photocured to form a protective layer, thereby preventing glass breakage, and Productivity in the process of forming the protective layer on the end face can be improved.

Claims (15)

A thiol compound (a) having two or more groups represented by the following general formula (1) in the molecule;
A polymerizable compound (b) having two or more allyl groups in the molecule;
A composition for reinforcing a glass end surface, comprising a photopolymerization initiator (c).

[In formula, R < ¹ > and R < ² > respectively independently represents a hydrogen atom, a C1-C10 alkyl group, or a C6-C10 aromatic group, and s represents the integer of 0-2. ] ^2. The composition for reinforcing a glass end surface according to claim 1, wherein either one or both of R ¹ and R ² is an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms. The glass end face reinforcing composition according to claim 1 or 2, wherein the thiol compound (a) is an ester compound of a mercapto-containing carboxylic acid represented by the following general formula (2) and a polyhydric alcohol.

[Wherein R ¹ , R ² and s are the same as those in the general formula (1). ]   The polyhydric alcohol may be branched alkylene glycol having 2 to 10 carbon atoms, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, cyclohexanediol, cyclohexanedimethanol , Norbornene dimethanol, 2,2-bis [4- (2-hydroxyethyloxy) phenyl] propane, hydrogenated bisphenol A, 4,4 ′-(9-fluorenylidene) bis (2-phenoxyethanol), and tris (2 The composition for reinforcing a glass end face according to claim 3, which is a kind selected from the group consisting of -hydroxyethyl) isocyanurate.   At least 1 type of the said polymeric compound (b) is a monomer (b-1) with a molecular weight of less than 500, The composition for glass end surface reinforcement as described in any one of Claims 1-4.   The composition for reinforcing a glass end surface according to claim 5, wherein the monomer (b-1) contains a compound having 2 to 4 allyl groups in the molecule.   The composition for reinforcing a glass end surface according to any one of claims 1 to 4, wherein at least one of the polymerizable compounds (b) contains an oligomer (b-2) having a molecular weight of 500 to 20000.   The composition for reinforcing a glass end surface according to claim 7, wherein the oligomer (b-2) contains a compound having 2 to 4 allyl groups in the molecule. The composition for reinforcing a glass end surface according to claim 7, wherein the oligomer (b-2) contains one or more compounds represented by the following general formulas (3), (4), and (5).

[Wherein, c is an integer of 1 to 5, R ³ is an alkylene group having 1 to 10 carbon atoms which may have an alkyl group having 1 to 5 carbon atoms as a substituent, and X is 1 carbon atom] A phenylene group or a cyclohexylene group optionally having an alkyl group of -4 as a substituent, and n is an integer of 0-20]

[Wherein c is the same as in the general formula (3), R ⁴ is an alkyl group having 1 to ⁴ carbon atoms or a group represented by the following formula (4 ′), and X is the general formula (3) ) And m is an integer from 3 to 70]

[Wherein c and X are the same as those in the general formula (4). ]

Wherein, c and X are the same as in the general formula (3), R ³ is the same as each R ³ independently in the general formula (3), p is an integer of from 1 to 10, q Is an integer from 5 to 50. ]   The glass according to any one of claims 7 to 9, wherein the polymerizable compound (b) includes a monomer (b-1) having a molecular weight of less than 500 and an oligomer (b-2) having a molecular weight of 500 to 20000. End face reinforcing composition.   The glass according to any one of claims 1 to 10, wherein the number of mercapto groups of the thiol compound (a) is 20 to 220 with respect to the number of terminal ethylenically unsaturated groups of the polymerizable compound (b). End face reinforcing composition.   Content of an organic solvent is 1 mass% or less, The composition for glass end surface reinforcement as described in any one of Claims 1-11 characterized by the above-mentioned.   Furthermore, the composition for glass end surface reinforcement | strengthening as described in any one of Claims 1-12 containing a coloring material.   The glass plate material in which the protective layer which consists of a hardened | cured material of the composition for glass end surface reinforcement as described in any one of Claims 1-13 is formed in the end surface of a glass member.   It is a manufacturing method of the glass plate material of Claim 14, Comprising: The process which cut | disconnects a glass base material and makes it a glass member, The end surface of the said glass member WHEREIN: It is any one of Claims 1-13. And a step of forming a protective layer by curing after applying the glass end face reinforcing composition.