KR20060082910A - Uv curable compositions showing flame retardancy to seal electrode from humidity in plasma display panel - Google Patents

Abstract

The present invention relates to an ultraviolet curable resin composition used to protect an electrode from moisture in the manufacture of a plasma display panel. The present invention is a urethane (meth) acrylate oligomer; Photocurable (meth) acrylate monomers; In the ultraviolet curable resin composition containing a photocuring agent, the urethane (meth) acrylate oligomer is a silane group-bonded urethane (meth) acrylate oligomer. The composition according to the present invention has a high adhesion to the display panel, has excellent water resistance and has a low moisture permeability and excellent flame retardancy.

PDP, water resistance, adhesion, resin composition, flame retardant, silane coupling, electrode protection

Description

UV curable compositions showing flame retardancy to seal electrode from humidity in plasma display panel}             

1 is a cross-sectional view showing a module when a plasma display panel and an adhesive are applied.

Explanation of symbols on the main parts of the drawings

1: electrode protective adhesive

2: glass plate

3: electrode

4: anisotropic conductive film

5: flexible print circuit

The present invention relates to an ultraviolet curable flame retardant resin composition (or adhesive) for electrode protection of a plasma display panel (PDP), and more particularly, to a urethane methacrylate oligomer or a urethane acrylate oligomer (hereinafter referred to as "urethane ( Meta) acrylate oligomer "; Photocurable methacrylate monomers or acrylate monomers (hereinafter referred to as "(meth) acrylate monomers"); The ultraviolet curable resin composition containing a photocuring agent WHEREIN: The said urethane (meth) acrylate oligomer is a silane group bonding type urethane (meth) acrylate oligomer, It is related with the ultraviolet curable resin composition for electrode protection of a plasma display panel. .

The present invention also relates to an ultraviolet curable resin composition for electrode protection of a plasma display panel having a flame retardant added to the composition and having excellent flame retardancy.

The figure of the module which applied the plasma display panel and the ultraviolet curable flame-retardant resin composition (adhesive agent) which concerns on this invention is shown in FIG. In the plasma display panel, the upper and lower plates are bonded to each other with an anisotropic conductive film interposed therebetween, and the electrode part of the lower plate and the flexible printed circuit board (FPC) part of the upper plate are electrically connected by the anisotropic conductive film in order to transmit electrical signals. Is supposed to work. At this time, the lower electrode part is composed of components such as silver, chromium, copper, aluminum, etc. according to the manufacturer, and when the plasma display panel is operated, they are oxidized when combined with moisture in the atmosphere as an electric signal is applied and a strong electric field is formed. Precipitating again and repeating these cycles, metal crystals grow slowly and eventually are connected to adjacent circuits and are discharged, resulting in defects in image realization and ultimately decreasing durability of the plasma display panel.

Accordingly, in order to block moisture that causes electrode oxidation, an adhesive is applied to the connection part between the flexible circuit board (FPC) and the upper and lower plates, and cured by ultraviolet rays to prevent moisture from penetrating, thereby causing precipitation due to corrosion of the electrode. (Hereinafter referred to as "migration") can be suppressed. Accordingly, the present invention relates to an ultraviolet curable flame retardant adhesive composition applied to protect an electrode of a plasma display panel from moisture. The physical properties required for the adhesive should be excellent in adhesion to the glass and the flexible circuit board (FPC), which are to be bonded to each other, to prevent the penetration of moisture by the interface, and after curing, the adhesive has low water permeability. It should be possible to prevent the penetration of moisture through. In particular, adhesion should be ensured not only at room temperature but also under conditions of high temperature and high humidity.

In order to achieve this purpose, conventionally, a method of applying a silicone moisture-curable adhesive to a required area and leaving it for a long time under constant conditions to cure by moisture is used.

However, when the silicone moisture curable adhesive is used, it requires a long time (24 hours) to completely cure, resulting in low productivity and excellent adhesion to glass due to the composition of silicon, but poor adhesion to FPC. It is easy to penetrate the water through, and the crosslinking density in the silicone structure is lower than that of the UV-curable adhesive, which also has the disadvantage of inferior in water permeability of the adhesive.

The present invention is to solve the problems of the conventional silicone moisture-curable resin composition as described above, to increase the adhesion to the plasma display panel substrate and lower the moisture permeability of the adhesive to prevent the ultraviolet curable resin composition Is to provide.

Another object of the present invention is to provide an ultraviolet curable flame retardant resin composition exhibiting excellent flame retardancy by adding a predetermined amount of flame retardant in order to impart flame retardance already possessed by the silicone moisture curable resin composition.

In general, polyurethane synthesized using diisocyanate and polyol is known to have excellent adhesion due to the cohesion and toughness peculiar to urethane. On the other hand, when exposed to moisture for a long time, there is a disadvantage that the urethane bond is decomposed by hydrolysis depending on the polyol used, and thus does not exert long time excellent initial physical properties. Accordingly, the present inventors started to develop a UV-curable resin composition based on urethane (meth) acrylate oligomers having suitable physical properties as an electrode protective adhesive for plasma display panels, and completed the present invention after a long period of research.

Polyurethane (meth) acrylate exhibits excellent cohesive force by constant hydrogen bond between molecules by isocyanate and polyol reacting with isocyanate and polyol in the molecule to show excellent cohesiveness, but it is easy to penetrate moisture and is exposed to moisture for a long time In case of penetration, the hydrogen bond is broken due to the penetration of water and some hydrolysis proceeds, resulting in a decrease in adhesion between molecules and a decrease in cohesion. Accordingly, in the present invention, by combining the appropriate molar silane coupling agent in the urethane oligomer, the silane group introduced therein reacts with the water to be absorbed and is substituted with a hydroxyl group to block the penetration of water into the adhesive, but rather to reduce the hydrogen bond due to the increase of the hydroxyl group. It prevented the reduction of adhesion even under the conditions of high temperature and high humidity, and achieved the physical properties of the low moisture permeability of the adhesive after curing as an ultraviolet curing resin composition for electrode protection of the plasma display panel.

Accordingly, the present invention can react with at least one polyol and diisocyanate to synthesize a urethane or urea prepolymer having a high-density urethane bond, thereby reacting with a certain mole of (meth) acrylate and water to induce ultraviolet curing. A certain molar silane coupling agent was reacted to synthesize a silane-linked urethane (meth) acrylate. In addition, after curing under certain conditions by mixing a predetermined amount of flame retardant with a photocurable monomer diluent and a photocuring agent to impart flame retardancy, the glass adhesive strength has a water transmittance of 100 g / cm ² or less at a thickness of 0.1mm while having an adhesive force of 20MPa or more A flame-retardant photocurable resin composition for plasma display panel electrode protection was obtained.

The ultraviolet curable flame-retardant resin composition for electrode protection of the plasma display panel of this invention is urethane (meth) acrylate oligomer; Photocurable (meth) acrylate monomer diluents; In the ultraviolet curable resin composition for electrode protection of a plasma display panel containing a photocuring agent, the urethane (meth) acrylate oligomer is a silane group-bonded urethane (meth) acrylate oligomer.

The ultraviolet curable flame retardant resin composition for electrode protection of the plasma display panel of the present invention may further contain a flame retardant in the composition.

In addition, UV-curable flame-retardant resin composition for electrode protection of the plasma display panel of the present invention is 10 to 90 parts by weight of the silane group-bonded urethane (meth) acrylate oligomer; 10 to 90 parts by weight of a photocurable (meth) acrylate monomer diluent; Characterized by including 1 to 10 parts by weight of a photocuring agent, the composition may further comprise 10 to 90 parts by weight of a flame retardant.

When the silane group-bonded urethane (meth) acrylate oligomer according to the present invention sets the diisocyanate and the polyol at a predetermined ratio, the polyol is added to the reactant containing the isocyanate when the NCO concentration of the reactants reaches the theoretical NCO concentration. After the reaction to synthesize a urethane oligomer (or urethane prepolymer), a small amount of a polymerization inhibitor is added to the urethane oligomer, and then the reaction rate may be slowed down by increasing the viscosity of the photocurable (meth) After adding the acrylate monomer diluent, the hydroxyl group-containing (meth) acrylate was slowly added, and then reacted until the NCO concentration of the reactant reached the theoretical NCO concentration while maintaining the reaction temperature at 60 to 80 ° C. Meta) acrylate oligomers are synthesized, and the oligomer contains an amine group. In the silane coupling agent, reaction of unreacted NCO of the coupling agent with an isocyanate to amine can be synthesized by introducing a silane at the terminal of the oligomer. After the reaction, the structure of the synthesized oligomer can be represented by the following general formula (I).

General formula (Ⅰ)

(Wherein R represents an alcohol group and m and n represent integers)

The silane group-bonded urethane (meth) acrylate oligomer according to the present invention preferably has a number average molecular weight in the range of 600 to 15,000. If the molecular weight of the oligomer is less than 600, the cohesive force of the oligomer is insufficient, and thus, after the preparation of the adhesive, This is because when UV curing, the adhesive force tends to be insufficient, and when the molecular weight of the oligomer exceeds 15,000, the viscosity of the oligomer is too high, which may cause difficulty in the mixing and mixing process during the preparation of the adhesive.

In addition, the silane group-bonded urethane (meth) acrylate oligomer according to the present invention is the presence of 2 to 12 urethane bonds per molecule. The urethane bond (or urea bond) in the molecule controls the reaction so that the number average molecular weight is polymerized in the range of 600 to 15,000 by reacting 1 to 1.67 moles of polyol having a molecular weight of 200 to 3,000 with 2 moles of diisocyanate. As a result, the number of urethane bonds per molecule can be introduced at an average density of 2 to 12.

There are various methods of introducing a double bond at the end of a urethane oligomer or urethane prepolymer synthesized by reacting diisocyanate with a polyol to induce an acrylic reaction by reaction with radicals generated from photoinitiators decomposed by ultraviolet light. However, as a preferable method, 0.1 to 1.9 mol of hydroxyl group-containing (meth) acrylate is added to and reacted with 1 mol of urethane prepolymer (prepolymer method), wherein the hydroxyl group-containing (meth) acrylate Is an alkyl group having 2 to 6 carbons, preferably 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, pentaerythritol It is preferable to use triacrylate, dipentaerythritol pentaacrylate, and the like.

As a coupling agent containing a silane group which is added after the reaction of the hydroxyl group-containing (meth) acrylate and reacted with the prepolymer, a 3-aminopropyltriethoxy having an amine group capable of bonding with a urethane at the terminal or a hydroxyl group Silane (3-aminopropyltriethoxy-silane), 3-aminopropyltrimethoxysilane, and the like.

Examples of the diisocyanate include isophorone diisocyanate, 2,4-toluene diisocyanate and isomers thereof, hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, 2,2-bis-4'-propane isocyanate, 6 Isopropyl-1,3-phenyldiisocyanate, bis (2-isocyanateethyl) -fumarate, 1,6-hexanediisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethylphenylene Diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,4-xylene diisocyanate , 1,3-xylene diisocyanate and the like can be used, preferably 2,4-toluene diisocyanate and its isomers, isophorone diisocyanate, 1,5-naphthalene diisocyanate , 1,4-xylene diisocyanate, 1,3-xylene diisocyanate or the like is better to use.

Polyols that react with isocyanates to form urethane bonds are monomolecular diols such as ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and neopentyl. Glycol, 1,4-cyclohexane dimethanol, bisphenol A, bisphenol F, reduced bisphenol A, reduced bisphenol F, dicyclopenta diol, tricyclodecanediol or a compound having three or more hydroxyl groups in the molecule, ie glycerol, trimethyl One or two or more selected from ethanol, trimethylolpropane, pentaerythritol, sorbose, and sorbitol can be used in combination.

As polyols, polyether polyols, polyester polyols, polycarbonate polyols or polycaprolactone polyols may be used alone or in combination, or may be used in combination with the above monomolecular diols.

Examples of the polyether polyols include copolymerized forms of polyethylene glycol, 1,2-polypropylene glycol, 1,3-polypropylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, and the like. Can,

Polyester polyols include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polytetramethylene glycol, tetramethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, Diols such as 1,4-cyclohexanedimethanol, 3-methyl-1,8-octanediol, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumalic acid, adipic acid, sebacic acid, etc. The polyester polyol of the form in which the acid of and the monomolecular diol reacted, or its copolymerization form can be illustrated.

The polycarbonate polyol may be exemplified by 1,6-hexane polycarbonate, and the polycaprolactone polyol may be ??-caprolactone and ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butanediol And diols such as 1,4-butanediol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol, and 1,4-cyclohexanedimethol The reacted form can be illustrated.

Among the ultraviolet curable acrylate monomers, as the monofunctional monomer, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, t-octyl (meth) acrylate, and N, N-dimethyl (meth) Acrylamide, N-vinylcaprolactam, N-vinylpyrrolidone, acryloyl morpholine, isobutoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, bonyl (meth) acrylate, isobonyl (meth ) Acrylic, tricyclotecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentadiene (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) ) Acrylate, ethoxyethoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol No (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, epoxydiethylene glycol (meth) acrylate, butoxyethyl (meth) acrylate, Tetrahydrofurfuryl (meth) acrylate, styryl (meth) acrylate, octadecyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, undecyl (meth) acrylate, Isodecyl (meth) acrylate, decyl (meth) acrylate, nonyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, octyl (meth) acrylate, heptyl (meth) ) Acrylate, hexyl (meth) acrylate, isoamyl (meth) acrylate, pentyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, amyl (meth) acrylate, Butyl (metal) Relate, Isopropyl (meth) acrylate, propyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth ) Acrylate, 2-hydroxyethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N'-dimethyl- Aminopropyl (meth) acrylate etc. can be illustrated,

As the polyfunctional monomer, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tripropylene Glycol diacrylate, trimethylolpropanetrioxyethyl (meth) acrylate, tricyclodecanedimethanol diacrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecanedimetha Nol di (meth) acrylate etc. can be illustrated.

The composition of the present invention requires a photocuring agent and used as an initiator 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenyl-acetophenone, xanthone, benzaldehyde, anthraquinone, 3-methyl Acetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoinethyl ether, 1- (4-isopropyl-phenol)- 2-hydroxy-2-methyl propane-1-one, thioxanthone, etc. can be illustrated,

Commercially available products include Irgacure 127, 184, 250, 369, 651, 500, 754, 784, 819, 819DW, 907, 1300, 1700, 1800, 2022, 2100, 2959 (Shibagai Corporation) and Darocure MBF, 1116. , 1173 (Merck Co.), 4265, TPO, Lucirine LR8728 (BASF Co., Ltd.), Ubecyl-936 (CBC), and the like, and among these, one kind or a mixture of two or more kinds can be used.

In addition, small amounts of photosensitizers such as diethylamine can also be added.

Flame retardants used to impart flame retardancy include dibromostyrene, polydibromostyrene, dibromostyrene copolymer, polybromostyrene, brominated polystyrene, tetrabromophthalate ester, tetrabromophthalic anhydride Ride, tetrabromophthalate diol, tetrabromophthalate diol mixture, tetrabromophthalate ester, tetrabromobenzoate ester, tetrabromobenzoate ester mixture, hexabromocyclododecane, tetrabromobisphenol A, tetra Bromobisphenol A bis (2,3-dibromopropyl ether), tetrabromobisphenol A bis allylether, tetrabromo bisphenol A phenoxy-terminated carbonane oligomer, decabromodiphenylethane, decabromodiphenyl Oxide, 2,4,6-tribromophenol, tribromophenyl allyl ether, bis tribromophenoxy Bromine series such as ethane, triaryl phosphate isopropylate, cresyl diphenyl phosphate, tricresyl phosphate, trizalyl phosphate, triphenyl phosphate, triaryl phosphate, lysosinol bis (diphenyl phosphate), bisphenol A bis Phosphate systems such as (diphenyl phosphate) and triaryl phosphate isopropylated, and antimony trioxide, magnesium oxide and aluminum oxide may be used as the metal-based flame retardant.

In addition, the UV-curable resin composition for protecting an electrode of the plasma display panel of the present invention may further include an antioxidant, a thermal polymerization inhibitor, a smoothing agent, an antifoaming agent, etc. in addition to the above composition.

For example, antioxidants are used to prevent yellowing by oxidizing when exposed to the outside after curing the adhesive for a long time. Irganox 1035 (Shibagai Corporation), Songnox (Songwon Industries) 1010, 1010F, 1076, 1076F, 2450, etc. Can be used,

The thermal polymerization inhibitor is to prevent the reaction from progressing and gelation during storage due to the generation of radicals by heat, and methyl ethyl hydroxy quinone, hydroquinone, etc. may be used.

Leveling agent is added to obtain uniform applicability when applying adhesive to display panel. BYK (Germany, Vik) 077, 085, 300, 301, 302, 306, 307, 308, 310, 315, 320, 322 , 323, 325, 330, 331, 332, 333, 335, 337, 341, 344, 345, 346, 347, 348, 352, 353, 354, 355, 356, 357, 358N, 359, 361N, 370, 371 , 373, 375, 380, 381, 390, 392, etc.,

Antifoaming agent is added for smooth removal of bubbles generated when applying adhesive to the panel by dispensing. BYK (Germany, Vik) A530, 011, 018, 019, 020, 021, 022, 023, 024, 025 , 028, 031, 032, 033, 034, 035, 036, 037, 038, 044, 045, 094, 1610, 1615, 051, 052, 053, 055, 057, 060N, 065, 066N, 067N, 070, 071 , 080, 088, 141 can be used.

Hereinafter, although an Example demonstrates this invention, this invention is not limited to the following Example.

EXAMPLE

<Synthesis Example 1>

Into a 3-liter round bottom flask with a stirrer was added 348.0 g (2 mole) of 2,4-toluene diisocyanate and 0.15 g of dibutyltindilaurate. After the reaction temperature was maintained at 70 ° C., 1000.0 g (1 mole) of polytetramethylene glycol having a number average molecular weight of 1000 was added to the reactor for 2 hours. After the addition was completed, the reactant was reacted until the NCO concentration of the reactant reached the theoretical NCO concentration to obtain a urethane prepolymer, and the reaction temperature was lowered to 50 ° C. and 1 g of methylhydroquinone was added as a polymerization inhibitor. Subsequently, the reaction rate may be slowed down by the increase of the viscosity. In order to increase the stirring effect, 337.0 g (20 weight ratio) of isobornyl acrylate is added to the reactive diluent, and 116.0 g (1 mole) of 2-hydroxyethyl acryl is added. The rate was slowly added to advance the reaction. After the completion of the addition, the reaction temperature was maintained at 70 ° C. for 2 hours until the NCO concentration of the reactants was reached until the theoretical NCO concentration was obtained to obtain an acryl-bonded urethane prepolymer. 221.37 g (1 mole) of aminopropyltriethoxysilane was added thereto, and a silane group was introduced at the terminal of the oligomer to synthesize a silane group-bonded urethane (meth) acrylate oligomer. The end of the reaction was confirmed by the disappearance of 2270cm ^-1 NCO peak by infrared spectroscopy, it can be seen that the silane group reacted with isocyanate, the number average molecular weight of the oligomer was 1,800g / mol using gel permeation chromatography (GPC) It was confirmed that the viscosity is 1,200 cps. In this way, it was found that a silane group-bonded urethane (meth) acrylate oligomer having an average urethane bond number of 4 according to the input ratio was synthesized.

<Synthesis Example 2>

In a 3 liter round bottom flask with a stirrer was placed 522.0 g (3 mole) of 2,4-toluene diisocyanate and 0.15 g of dibutyltindilaurate. After the reaction temperature was maintained at 70 ° C., 2000.0 g (2 moles) of polytetramethylene glycol having a number average molecular weight of 1000 was added to the reactor for 2 hours. After completion of the addition, the reactant was reacted until the NCO concentration of the reactant reached the theoretical NCO concentration to obtain a urethane prepolymer, and the reaction temperature was lowered to 50 ° C. and 1 g of methylhydroquinone was added as a polymerization inhibitor. Subsequently, the reaction rate may be slowed down by the increase of the viscosity. In order to increase the stirring effect, 630.5 g (20 weight ratio) of isobornyl acrylate is added to the reactive diluent and 116.0 g (1 mole) of 2-hydroxyethyl acrylate is added. The reaction was allowed to proceed slowly. After the completion of the input, the reaction temperature was maintained at 70 ° C. for 2 hours until the NCO concentration of the reactants was reached until the theoretical NCO concentration was obtained to obtain an acrylic bonded urethane prepolymer, and the reaction temperature was lowered to 50 ° C. and 3- 221.37 g (1 mole) of aminopropyltriethoxysilane was added thereto, and a silane group was introduced at the terminal of the oligomer to synthesize a silane group-bonded urethane (meth) acrylate oligomer. The end of the reaction was confirmed that the 2700cm ^-1 NCO peak disappeared by infrared spectroscopy, indicating that the silane group reacted with isocyanate. The number average molecular weight of the oligomer was 3,100 g / mol using gel permeation chromatography (GPC). It was confirmed that the viscosity was 4,200 cps. Thus, it was found that a silane group-bonded urethane (meth) acrylate oligomer having an average urethane bond number of 6 according to the input ratio was synthesized.

Example 1

Into a reactor equipped with a stirrer, 60 g (g) of the silane group-bonded urethane acrylate oligomer synthesized in Synthesis Example 1 was added, 20 g (g) of hexanediol diacrylate, 15 g (g) of ethylhexyl acrylate, and an antifoaming agent (BYK 020) 0.5 grams (g), 0.5 grams (g) of methyl hydroquinone as a polymerization inhibitor, and 4 grams (g) of a photocuring agent (Irgacure 184 (Shibagai Corporation)) were added. 20 grams (g) of tetrabromophthalic anhydride) was added and blended at room temperature with stirring at 400 rpm for 30 minutes. An ultraviolet curable resin composition for protecting an electrode of a plasma display panel according to the present invention was obtained as a transparent liquid composition having a viscosity of 4,000 cps at 25 ° C.

Example 2

Into a reactor equipped with a stirrer, 60 grams (g) of the silane group-bonded urethane acrylate oligomer synthesized in Synthesis Example 2 was added, 20 grams (g) of hexanediol diacrylate, and 15 grams (g) of ethylhexylacryl. 0.5 gram (g) of methylhydroquinone was added as a rate, 0.5 gram (g) antifoaming agent (BYK 020), and a polymerization inhibitor. As a photocuring agent, 4.0 grams (g) of Irgacure 184 (Shibagai Co., Ltd.) was added, and 20 grams (g) of flame retardant (tetrabromophthalic anhydride) was added to impart flame retardancy, and stirred at 400 rpm for 30 minutes at room temperature. Blending. A clear liquid composition having a viscosity of 5,000 cps at 25 ° C. was obtained and the physical properties of the adhesive were measured by the method illustrated in Formulation Example 1.

[Comparative Example]

<Synthesis Example 3>

Into a 3-liter round bottom flask with a stirrer was added 348.0 g (2 mole) of 2,4-toluene diisocyanate and 0.15 g of dibutyltindilaurate. After the reaction temperature was maintained at 70 ° C., 1000.0 g (1 mole) of polytetramethylene glycol having a number average molecular weight of 1000 was added to the reactor for 2 hours. After the completion of the addition, the reaction was allowed to react until the NCO concentration of the reactant reached the theoretical NCO concentration, and then the reaction temperature was lowered to 50 ° C. and 1 g of methylhydroquinone was added as a polymerization inhibitor. Subsequently, the reaction rate may be slowed down by the increase of the viscosity. In order to increase the stirring effect, 337.0 g (20 weight ratio) of isobornyl acrylate is added to the reactive diluent and 232.0 g (2 mole) 2-hydroxyethyl acrylate is added. The reaction was allowed to proceed slowly. For 3 hours after the end of the reaction, the reaction temperature was maintained at 70 ° C until the NCO concentration of the reactant reached the theoretical NCO concentration, and the reaction was terminated by confirming the disappearance of 2270cm ^-1 NCO peak by infrared spectroscopy. Terminated. At this time, the synthesized oligomer has a molecular weight of 1700 g / mol, a viscosity of 1320 cps, and a number of urethane bonds of 4.

<Synthesis Example 4>

In a 3 liter round bottom flask with a stirrer was placed 522.0 g (3 mole) of 2,4-toluene diisocyanate and 0.15 g of dibutyltindilaurate. After the reaction temperature was maintained at 70 ° C., 2000.0 g (2 moles) of polytetramethylene glycol having a number average molecular weight of 1000 was added to the reactor for 2 hours. After the addition was completed, the reaction was allowed to react until the NCO concentration of the reactant reached the theoretical NCO concentration, and then the reaction temperature was lowered to 50 ° C. and 1 g of methylhydroquinone was added as a polymerization inhibitor. Subsequently, the reaction rate may be slowed down due to the increase in viscosity. In order to increase the stirring effect, 630.5 g (20 weight ratio) of isobornyl acrylate is added to the reactive diluent and 232.0 g (2 mole) 2-hydroxyethyl acrylate is added. The reaction was allowed to proceed slowly. For 2 hours after the end of the reaction, the reaction temperature was maintained at 70 ° C until the NCO concentration of the reactant reached the theoretical NCO concentration. The reaction was terminated by confirming the disappearance of 2270cm ^-1 NCO peak by infrared spectroscopy. Terminated. At this time, the synthesized oligomer has a molecular weight of 3,200 g / mol, a viscosity of 5,200 cps and a urethane bond number of 4.

<Synthesis Example 5>

Into a 3-liter round bottom flask with a stirrer was added 348.0 g (2 mole) of 2,4-toluene diisocyanate and 0.15 g of dibutyltindilaurate. After the reaction temperature was maintained at 70 ° C., 62.0 g (1 mole) of ethylene glycol having a molecular weight of 62 g / mol or less and 200 was added to the reactor for 2 hours. After the addition was completed, the reactant was reacted until the NCO concentration of the reactant reached the theoretical NCO concentration to obtain a urethane prepolymer, and the reaction temperature was lowered to 50 ° C. and 1 g of methylhydroquinone was added as a polymerization inhibitor. Subsequently, the reaction rate may be slowed down by the increase of the viscosity. In order to increase the stirring effect, 186.0 g (20 weight ratio) of isobornyl acrylate is added to the reactive diluent, and 116.0 g (1 mole) 2-hydroxyethyl acryl is added. The rate was slowly added to advance the reaction. After the completion of the input, the reaction temperature was maintained at 70 ° C. for 2 hours until the NCO concentration of the reactants was reached until the theoretical NCO concentration was obtained to obtain an acrylic bonded urethane prepolymer, and the reaction temperature was lowered to 50 ° C. and 3- 221.37 g (1 mole) of aminopropyltriethoxysilane was added thereto, and a silane group was introduced at the terminal of the oligomer to synthesize a silane group-bonded urethane (meth) acrylate oligomer. The end of the reaction was confirmed that the disappearance of 2270cm ^-1 NCO peak by infrared spectroscopy showed that the silane group reacted with isocyanate, and the number average molecular weight of oligomer was 510g / mol using gel permeation chromatography (GPC). The viscosity is 1,500 cps. In this way, it was found that a silane group-bonded urethane (meth) acrylate oligomer having an average urethane bond number of 4 according to the input ratio was synthesized.

<Synthesis Example 6>

Into a 20 liter round bottom flask with a stirrer was charged 1044.0 g (6 mole) of 2,4-toluene diisocyanate and 0.45 g of dibutyltindilaurate. After the reaction temperature was maintained at 70 ° C, 15,000 g (5 mole) of polytetramethylene glycol having a number average molecular weight of 3000 was added to the reactor for 2 hours. After the addition was completed, the reactant was reacted until the NCO concentration of the reactant reached the theoretical NCO concentration to obtain a urethane prepolymer. The reaction temperature was lowered to 50 ° C., and 1 g of methylhydroquinone was added as a polymerization inhibitor. Subsequently, since the reaction rate may be slowed down by the increase of the viscosity, 4095.0 g (20 molar ratio) of isobornyl acrylate is added to the reaction diluent to increase the stirring effect, and 116.0 g (1 mole) of 2-hydroxyethyl The reaction was advanced by slowly adding acrylate. After the completion of the input, the reaction temperature was maintained at 70 ° C. for 2 hours until the NCO concentration of the reactants was reached until the theoretical NCO concentration was obtained to obtain an acrylic bonded urethane prepolymer, and the reaction temperature was lowered to 50 ° C. and 3- 221.37 g (1 mole) of aminopropyltriethoxysilane was added thereto, and a silane group was introduced at the terminal of the oligomer to synthesize a silane group-bonded urethane (meth) acrylate oligomer. The end of the reaction was confirmed by the disappearance of 2270cm ^-1 NCO peak by infrared spectroscopy, it can be seen that the silane group reacted with isocyanate, the number average molecular weight of the oligomer was 16,300g / mol using gel permeation chromatography (GPC) It was confirmed that the viscosity is 81,300 cps. Thus, it was found that a silane group-bonded urethane (meth) acrylate oligomer having an average urethane bond number of 12 according to the input ratio was synthesized.

However, the viscosity of the oligomer was too high at 81,300 cps, making it impossible to apply with this adhesive.

Comparative Example 1

Oligomeric Synthesis 60 g (g) of the urethane acrylate oligomer synthesized in Synthesis Example 3 was added to a reactor with a stirrer, 20 g (g) hexanediol diacrylate, 15 g (g) ethylhexyl acrylate, 0.5 grams (g) of methylhydroquinone was added as an antifoaming agent (BYK 020) and a polymerization inhibitor. As a photocuring agent, 4.0 grams (g) of Irgacure 184 (Sibaga Igisa) was added, and 20 grams (g) of flame retardant (tetrabromophthalic anhydride) was added to give flame retardancy, and at 400 rpm for 30 minutes at room temperature. It mix | blended while stirring. A clear liquid composition having a viscosity of 5,000 cps at 25 ° C. was obtained and the physical properties of the adhesive were measured by the method illustrated in Example 1.

Comparative Example 2

Oligomeric Synthesis 60 g (g) of the urethane acrylate oligomer synthesized in Synthesis Example 4 was added to a reactor with a stirrer, 20 g (g) hexanediol diacrylate, 15 g (g) ethylhexyl acrylate, 0.5 0.5 gram (g) of methylhydroquinone was added as a gram (g) antifoaming agent (BYK 020) and a polymerization inhibitor. As a photocuring agent, 4.0 grams (g) of Irgacure 184 (Shibagai Co., Ltd.) was added, and 20 grams (g) of flame retardant (tetrabromophthalic anhydride) was added to impart flame retardancy, and stirred at 400 rpm for 30 minutes at room temperature. Blending. A clear liquid composition having a viscosity of 5800 cps at 25 ° C. was obtained and the physical properties of the adhesive were measured by the method illustrated in Example 1.

Comparative Example 3

Oligomeric Synthesis 60 g (g) of the urethane acrylate oligomer synthesized in Synthesis Example 5 was added to a reactor with a stirrer, 20 g (g) hexanediol diacrylate, 15 g (g) ethylhexyl acrylate, 0.5 0.5 gram (g) of methylhydroquinone was added as a gram (g) antifoaming agent (BYK 020) and a polymerization inhibitor. As a photocuring agent, 4.0 grams (g) of Irgacure 184 (Sibaga Igisa) was added, and 20 grams (g) of flame retardant (tetrabromophthalic anhydride) was added to give flame retardancy, and at 400 rpm for 30 minutes at room temperature. It mix | blended while stirring. A transparent liquid composition having a viscosity of 4200 cps at 25 ° C. was obtained, and the physical properties of the adhesive were measured by the method illustrated in Example 1, and the results of the above experiments are shown in Table 2 below.

[Comparative Example 4]

Oligomeric Synthesis 60 g (g) of the urethane acrylate oligomer synthesized in Synthesis Example 6 was added to a reactor with a stirrer, 20 g (g) hexanediol diacrylate, 15 g (g) ethylhexyl acrylate, 0.5 0.5 gram (g) of methylhydroquinone was added as a gram (g) antifoaming agent (BYK 020) and a polymerization inhibitor. As a photocuring agent, 4.0 grams (g) of Irgacure 184 (Shibagai Co., Ltd.) was added, and 20 grams (g) of flame retardant (tetrabromophthalic anhydride) was added to impart flame retardancy, and stirred at 400 rpm for 30 minutes at room temperature. Blending. A transparent liquid composition having a viscosity of 32,000 cps at 25 ° C. was obtained, and the physical properties of the adhesive were measured by the method illustrated in Example 1, and the results of the above experiments are shown in Table 2 below.

<Property test>

The physical properties of the liquid compositions obtained in Examples and Comparative Examples were measured by the following methods. At this time, the test method for measuring the physical properties of the resin composition according to the present invention is intended to block moisture inducing migration of the silver electrode, and thus, it is allowed to stand for a certain period of time in a constant temperature and humidity condition of adhesion and high temperature and high humidity conditions. Then, the adhesive force was measured to measure the blocking force of the water absorbed into the interface, and after curing the resin composition (adhesive) to a predetermined thickness, the moisture permeability was measured to evaluate the blocking force against the water passing through the adhesive. In addition, to evaluate the flame retardancy, the flame retardancy of the adhesive after curing was evaluated according to the flame retardancy evaluation criteria specified in the UL standard.

① adhesion

Each of the resin compositions of Examples 1 and 2 and Comparative Examples 1 to 3 was coated with 1 cm X 10 cm in a thickness of 1 mm on a glass plate of 3 cm X 10 cm, and then irradiated with 3.0 J / cm ² in an ultraviolet curing machine to prepare five adhesive specimens, respectively. It was. Adhesion at room temperature and humidity is 25 ℃, 30% RH, and adhesion at high temperature and humidity is obtained after storing the prepared test specimen at 75 ℃ and 95% RH for 72 hours, and then at 25 ℃ and 30% RH. In accordance with the 180 ^° peel test method using an Instron tensile tester and the results are shown in Table 2 below. Five adhesive specimens of each of the prepared examples and comparative examples were subjected to a 180 ^° peel test to obtain an average value thereof, and were calculated as adhesive strength.

② Moisture Vapor Transmission Rate (MVTR)

After curing the moisture-permeable cup containing calcium chloride (CaCl ₂ ) with the resin compositions of Examples 1 and 2 and Comparative Examples 1 to 3, and then covered with a thickness of 0.1 mm, the initial weight was measured and measured at 40 ° C. and 85% RH. After storage for 24 hours, the weight was measured to measure the moisture permeability for 24 hours and the results are shown in Table 2 below.

③ flame retardant

Each of the resin compositions of Examples 1, 2 and Comparative Examples 1 to 3 was filled in a mold having a width of 10 mm, a length of 100 mm, and a thickness of 3 mm, and then irradiated at 3.0 J / cm ² in an ultraviolet curing machine to prepare 10 specimens. Thus prepared specimen was burned under the test conditions according to the UL standards to measure the flame retardancy and the results are shown in Table 2 below.

Exam conditions :

1) Place the specimen vertically in a 1/4 "(0.635 cm) position and install a medical gauze screen under 12" (30.48 cm)

2) A 3/4 "(1.905 cm) long blue flame is ignited from the bottom toward the bottom edge of the specimen at a distance of 3/8" (0.9524 cm).

3) Keep the flame for 10 seconds, then remove the flame and record the burning time of the specimen

4) Immediately after combustion stops, ignite the flame again for 10 seconds, remove the flame, and then record the combustion time and the time after which the afterglow remains.

UL 94 V-0 rating

1) The burner's flame is removed during the first ignition and none of the five specimens have been burned.

2) Combustion time does not exceed 50 seconds among 10 total ignition experiments

3) No flame or afterglow reaches the clamp that holds the specimen while the experiment is in progress

4) When no specimen has a burning time of afterglow exceeding 30 seconds

UL 94 V-1 rating

1) After the burner flame has been removed, no specimen has burned for more than 10 seconds.

2) If the total combustion time does not exceed 250 seconds during 10 total ignition experiments

3) If there is no sample dropping a piece of fire on the metal net installed below during the experiment

4) If no specimen reaches flame or afterglow until the clamp

5) no sample afterglow exceeds 60 seconds

UL 94 V-2 rating

1) After the burner flame has been removed, no specimen has burned for more than 130 seconds.

2) If the total combustion time does not exceed 250 seconds during 10 total ignition experiments

3) If no specimen reaches flame or afterglow until the clamp

4) The fired fragments fall out of the specimen due to sudden, non-continuous combustion.

5) no sample afterglow exceeds 60 seconds

6) If no specimen reaches flame or afterglow until the clamp

7) no sample with afterglow exceeding 60 seconds

division                                              Viscosity (cps) Molecular Weight (g / mol) Urethane Bonded Water Synthesis Example 1                                              1,200 1,800 4 Synthesis Example 2                                              4,200 3,100 6 Synthesis Example 3                                              1,320 1,700 4 Synthesis Example 4                                              5,200 3,200 6 Synthesis Example 5                                              1,500 510 4 Synthesis Example 6                                              81,300 16,300 12

 division Adhesive force (MPa)                                               Moisture permeability (0.1mm, g / ㎠)  Flame retardant  Viscosity (cps) Room temperature and humidity                                              High temperature, high humidity Example 1                                              35.0 30.2 88.3 V-2 4,000 Example 2                                              32.0 28.4 91.5 V-2 5,000 Comparative Example 1                                              12.0 2.0 250.2 V-2 5,000 Comparative Example 2                                              10.3 1.2 280.2 V-2 5,800 Comparative Example 3                                              13.1 12.1 92.3 V-2 4,200 Comparative Example 4                                              31.2 29.4 98.2 V-2 32,000

As shown in Table 1, the oligomer of Synthesis Example 6 having a molecular weight of more than 15,000 g / mol has a problem that dispensing does not occur when applied as an adhesive because the viscosity is too high, and thus it is not suitable for this use.

In addition, as shown in Table 2, when using the oligomer developed in the present invention, the adhesion force with glass required to protect the electrode of the plasma display panel from moisture shows a value of 30 MPa or more at room temperature and humidity, and at high temperature and high humidity. It can be seen that the decrease in adhesion is small even under the condition of.

On the other hand, as shown in Comparative Example 1 and Comparative Example 2, when the oligomer which does not introduce a silane group into the oligomer, that is, when all of the sock ends of the isocyanates are mixed using a general oligomer having an acryl group, the adhesive force is lowered as a whole, especially high temperature and high humidity. It can be seen that the adhesive force under the conditions drops sharply. And in the case of the oligomer whose molecular weight is less than 600 like the comparative example 3, it turns out that even after a hardening, the wettability to a to-be-adhered object is lacking and even the normal temperature and humidity adhesive strength falls remarkably. In addition, the moisture permeability of the oligomer incorporating the silane group was also low in terms of moisture permeability, which satisfies the requirements of the adhesive for protecting the electrode from moisture. In the case of Comparative Example 4 is satisfied in terms of physical properties after curing, but the viscosity of the oligomer is high, the viscosity of the formulation is also high, there is a difficulty in dispensing.

As a result of the above results, since the UV-curable resin composition for electrode protection of the plasma display developed in the present invention shows an excellent effect on blocking glass adhesion and moisture permeation, the liquid composition of the present invention is used for protecting the electrode from moisture. It is very suitable for.

Claims (10)

Urethane (meth) acrylate oligomers; Photocurable (meth) acrylate monomer diluents; In the ultraviolet curable resin composition containing a photocuring agent, The urethane (meth) acrylate oligomer is a silane group-bonded urethane (meth) acrylate oligomer, UV curable flame-retardant resin composition for electrode protection of a plasma display panel. The method of claim 1, The silane group-bonded urethane (meth) acrylate oligomer is a compound represented by the following general formula (I): UV-curable flame-retardant resin composition for electrode protection of a plasma display panel. General formula (Ⅰ)

(Wherein R represents an alcohol group and m and n represent integers) The method of claim 1, UV-curable resin composition for electrode protection of the plasma display panel, characterized in that the silane group-bonded urethane (meth) acrylate oligomer has a number average molecular weight of 600 to 15,000. The method of claim 1, Ultraviolet curable resin composition for electrode protection of a plasma display panel, characterized in that the silane group-bonded urethane (meth) acrylate oligomer has 2 to 12 urethane bonds per molecule. The method of claim 1, The silane group-bonded urethane (meth) acrylate oligomer is a diisocyanate compound; Mixtures of one or more polyols having a molecular weight of 200 to 3,000; And (meth) acrylate compound which has a hydroxyl group; A silane group-bonded urethane (meth) acrylate oligomer having a number-average molecular weight of 600 to 15,000 and a urethane bond in the range of 2 to 12 in a molecule thereof by reacting a silane coupling agent capable of reacting with an isocyanate having an amine group at a constant ratio. The ultraviolet curable resin composition for electrode protection of a plasma display panel characterized by the above-mentioned. The method according to any one of claims 1 to 5, UV-curable resin composition for electrode protection of the plasma display panel is 10 to 90 parts by weight of the silane group-bonded urethane (meth) acrylate oligomer; 10 to 90 parts by weight of a photocurable (meth) acrylate monomer diluent; And 1 to 10 parts by weight of a photocuring agent. The method of claim 6, The UV curable resin composition has a glass adhesive strength of 20MPa or more, and a moisture permeability of 0.1 mm (mm) at a thickness of 100 grams per square centimeter (g / cm 2) or less, UV curable resin composition for electrode protection of a plasma display panel. The method according to any one of claims 1 to 5, An ultraviolet curable flame retardant resin composition for electrode protection of a plasma display panel, wherein the ultraviolet curable flame retardant resin composition for electrode protection of the plasma display panel further contains a flame retardant. The method of claim 8, UV-curable resin composition for electrode protection of the plasma display panel is 10 to 90 parts by weight of the silane group-bonded urethane (meth) acrylate oligomer; 10 to 90 parts by weight of a photocurable (meth) acrylate monomer diluent; 1 to 10 parts by weight of a photocuring agent; And 10 to 90 parts by weight of a flame retardant, an ultraviolet curable resin composition for protecting an electrode of a plasma display panel. The electrode of a plasma display panel according to claim 9, wherein the UV curable resin composition has a glass adhesive strength of 20 MPa or more and a water permeability of 0.1 millimeter (mm) at a thickness of 100 grams per square centimeter (g / cm 2) or less. UV curable resin composition for protection.

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