KR101611934B1 - Radiation curable resin composition - Google Patents

Abstract

According to one aspect of the present invention, there is provided a resin composition comprising: (A) a polymer resin; (B) an unsaturated compound for adjusting the refractive index; (C) a hydrogen donor-containing photoinitiator; And (D) a hydrogen donor-containing unsaturated compound.

Description

Radiation curable resin composition [0002]

The present invention relates to a radiation curable resin composition.

In recent years, the mounting of touch panels on display bodies such as LCDs, OLEDs, and LEDs has become mainstream, and direct bonding has been performed between the touch panels and displays. In addition, in the mounted touch panel, there is a situation in which the connection between the screen and the touch panel, the connection between the icon sheet and the touch panel, the bonding between the transparent substrate and the transparent plate for forming the transparent electrode, Are required to have improved visibility, and are required to have overall durability such as moisture impregnation, vibration proofness, impact resistance and the like, particularly in displays used for aviation and shipping. In the technique using such a bonding material, the adhesiveness must basically be satisfied, and there is a lack of improvement in performance due to optically high transmittance, refractive index inconsistency between the display body and the touch panel or between the optical functional materials, and therefore, refractive index matching . In addition, in the photocuring process of the bonding process between the touch panel and the display body, there is a portion that is not lighted depending on the device structure, and efficient curing of such portions is required.

The present invention provides a transparent composition that exhibits the above-described characteristics and exhibits efficient curing properties and can control the refractive index, and a photosensitive composition capable of exhibiting effective photo-curing properties in an unexposed area.

According to one aspect of the present invention, there is provided a resin composition comprising: (A) a polymer resin; (B) an unsaturated compound for adjusting the refractive index; (C) a hydrogen donor-containing photoinitiator; And (D) a hydrogen donor-containing unsaturated compound.

According to another aspect of the present invention, there is provided a resin composition comprising: (A) a polymer resin; (B) an unsaturated compound for adjusting the refractive index; (C) a hydrogen donor-containing photoinitiator selected from the following formulas (5) or (6); And (D) a (meth) acrylic compound containing at least one hydrogen donor selected from the group consisting of a hydroxyl group, a carboxyl group, an amine group and a thiol group.

[Chemical Formula 5]

[Chemical Formula 6]

According to still another aspect of the present invention, there is provided a cured film produced by curing the above radiation curable resin composition.

When the radiation curable resin composition of the present invention is used in a bonding process between a touch panel and a display, it is easy to control a desired specific refractive index and has a high transmittance without yellowing. In the photo-curing process, the photo-curing property is improved to the part where light is not received according to the device structure, and at the same time, the curing speed is fast. Therefore, the module is not cured by over- Can be reduced. In particular, it has excellent light-curing properties when applied to a thick film having a thickness of 150 to 200 mu m between modules.

Hereinafter, each component of the radiation curable resin composition of the present invention will be described in more detail.

(A) Polymer resin

In the radiation curable resin composition of the present invention, the polymer resin plays a role of controlling physical properties such as hardness, elasticity, bending property and ductility of a film formed after curing. As the polymer resin, a (meth) acrylate copolymer is mainly used. Depending on the use, a polymer such as polyisoprene, polybutadiene, polyurethane, polyester, polyimide, polyamic acid, polyimide including sulfur, polysiloxane Resin can be used, but it is not limited to the above-mentioned polymer resin.

Preferably, the polymer resin in the whole composition may be contained in an amount of 20 to 80% by weight. In this range, it is possible to control the physical properties required in forming the adhesive film.

(B) an unsaturated compound for controlling the refractive index

The unsaturated compound for controlling the refractive index serves to adjust the refractive index of the cured film formed by the curing of the entire composition to perform the refractive index matching between the optical materials to be bonded. The refractive index of the desired final cured film can be achieved by adjusting the amount of the unsaturated compound having various refractive indexes in the radiation curable resin composition for controlling the refractive index. The unsaturated compound for controlling the refractive index may have the form of a monomer or an oligomer containing an ethylenic unsaturated group. Preferably, the refractive index-controlling unsaturated compound may be a (meth) acrylic monomer. The (meth) acrylic monomer may have a refractive index of about 1.40 to 1.68 depending on the kind. Specifically, the unsaturated compound for controlling the refractive index is selected from the group consisting of pentaerythritol acrylate, dicyclopentanyl (meth) acrylate, isobonyl (meth) acrylate, bisphenol acrylate, bisphenol epoxy acrylate, fluorene acrylate, urethane acrylate, (For example, pentaerythritol tetrakis (3-mercaptopropionate)), and the like, but is not limited thereto. Preferably, the acrylate containing sulfur has a very high atomic refractive index of sulfur, so that the refractive index of the cured film can be easily controlled even in a small amount. The refractive index of the cured product of the entire composition after curing can be controlled within the range of 1.45 to 1.65 by the unsaturated compound for controlling the refractive index.

In the whole composition, 5 to 70% by weight, preferably 10 to 50% by weight, of the unsaturated compound for controlling refractive index can be used. If it is less than the above range, it may not affect the refractive index change, and if it exceeds the above range, the physical properties of the adhesive film may be deteriorated.

(C) Hydrogen donor-containing photoinitiator

The hydrogen donor-containing photoinitiator contains a hydrogen donor in the molecule so as to have a radical diffusion function capable of effectively photo-curing the region not receiving light at various thicknesses. The hydrogen donor is -OH, -COOH, -NH ₂ Or -SH functional groups, of which at least one functional group may be included in the photoinitiator structure. The hydrogen donor serves to control the concentration of the relative radicals of the radicals that preferentially participate in the curing reaction among the two radicals generated as the initiating reaction of the photoinitiator proceeds. Thus, by inhibiting radical-radicals, radicals participating in the photo-curing reaction can be efficiently produced.

The type of the photoinitiator is not particularly limited, but an oxime ester photoinitiator or a ketone photoinitiator is preferable in terms of strength of bond dissociation energy. Although the position of the hydrogen donor is not particularly limited, it is preferable that the hydrogen donor is present at the alpha carbon position of the C = O bond and the C = N bond in terms of radical capture efficiency. The photoinitiator may have the structure of an oxime ester system represented by the following formula (1) or (2) or a ketone system photoinitiator represented by the above formula (3) or (4)

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

In the above Chemical Formulas 1 to 4 Hy is a hydrogen donor, -OH, -COOH, -NH ₂ Or -SH functional group. Preferably Hy is -OH in terms of ease of synthesis.

And X is -CR'R "-, -O-, -S- or -Se-, and R 'and R" are each independently hydrogen or methyl.

R ₁ to R ₈ are each independently selected from the group consisting of hydrogen, halogen, amino, nitro, cyano, hydroxy, substituted or unsubstituted C ₁ -C ₃₀ alkyl, substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl, Or unsubstituted C ₁ -C ₃₀ alkoxy, substituted or unsubstituted C ₆ -C ₃₀ aryl, substituted or unsubstituted C ₆ -C ₃₀ aralkyl, substituted or unsubstituted C ₁ -C ₃₀ hetero Alkyl, substituted or unsubstituted C ₂ -C ₃₀ heterocycloalkyl, substituted or unsubstituted C ₅ -C ₃₀ heteroaryl, substituted or unsubstituted C ₅ -C ₃₀ heteroaralkyl. Adjacent substituents may also be linked together to form a C ₅ -C ₁₀ ring.

"Substituted" in the expression " substituted or unsubstituted ", as used herein, means that at least one hydrogen atom in the hydrocarbon is each independently replaced with the same or different substituents. Useful substituents include -F, -Cl, -Br, -CN, -NO 2, -OH, -NH 2 , but is not limited thereto.

More specifically, the oxime ester-based photoinitiator may be selected from, for example, one of the structural formulas shown by the following formula (5).

[Chemical Formula 5]

The ketone-based photoinitiator may be selected from, for example, one of the structural formulas shown by the following formula (6).

[Chemical Formula 6]

In the photoinitiator of the present invention, oxime ester-based photoinitiators can be selected from the viewpoint of having an N-O bond having a lower dissociation energy than the C-C bond of the ketone-based initiator.

The photoinitiator may be used in admixture with one or more other photoinitiators containing a hydrogen donor, if necessary, or in combination with one or more other photoinitiators that do not contain a hydrogen donor. Another photoinitiator that does not contain a hydrogen donor is not particularly limited as long as it can react with a (meth) acrylic compound to form a crosslinked structure through ultraviolet irradiation or the like. Examples of such known photoinitiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2 , 2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy- Propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2- ) Ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2- Anthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylketal, acetophenone dimethylketal, p-dimethylamino Methylbenzyl-phenyl] propanone] and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the like can be given. have.

In the whole composition, 0.5 to 10% by weight, preferably 1 to 7% by weight, of the photoinitiator may be used. If the amount is less than the above range, the photocuring may not be performed well, and if it exceeds the above range, the solubility may be lowered, or in the case of a thick film, only surface hardening may occur.

(D) Hydrogen donor-containing unsaturated compound

An unsaturated compound containing a hydrogen donor such as a hydroxyl group, a carboxyl group, an amine group or a thiol group in the molecule may be a monomer or an oligomer having simultaneously an ethylenically unsaturated group capable of participating in the curing reaction.

 The hydrogen donor-containing unsaturated compound has an unsaturated bond and a hydrogen donor at the same time. As a result, it has a function of controlling the degree of photo-curing and suppressing radical-radicals.

When the hydrogen donor-containing unsaturated compound is used together with the hydrogen donor-containing photoinitiator, the degree of hardening control and the radical diffusion effect can be increased. The hydrogen donor-containing unsaturated compound may be a (meth) acrylic compound containing a hydrogen donor.

Examples of the hydroxyl group-containing (meth) acryl compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 6-hydroxyhexyl (meth) Mono (meth) acrylates of alkylenediols such as butyl (meth) acrylate, butyl (meth) acrylate, isopropyl (meth) acrylate, butyl (Meth) acrylamides such as N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide and the like, and these may be used singly or in combination.

The (meth) acrylic compound containing a carboxyl group is not particularly limited as long as it is a (meth) acrylic compound having a carboxyl group, and examples thereof include (meth) acrylic acid,? -Ethylacrylic acid, crotonic acid,? -Methyl crotonic acid, Adduct of unsaturated aliphatic monocarboxylic acids such as isocrotonic acid, tiglic acid and angelic acid; And adducted unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid and dihydromuconic acid, and the like, and these may be used alone or in combination.

As the hydrogen donor-containing unsaturated compound, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl , 4 '- (propane-2-diyl) bis (2- (allyloxy) phenol) desirable.

The hydrogen donor-containing unsaturated compound in the whole composition may be used in an amount of 1 to 40% by weight, preferably 2 to 20% by weight. Below the above range, the desired function may not be exhibited, and above the above range, the solubility or the curing density may be lowered.

(E) a (meth) acrylic compound

The radiation curable resin composition of the present invention may further contain a (meth) acrylic compound for controlling viscosity. When the viscosity-modifying (meth) acrylic compound is used in the radiation curable resin composition of the present invention in a solventless form, the viscosity and adhesion properties of the composition can be controlled.

The (meth) acrylic compound for controlling viscosity may contain 1 to 4 unsaturated groups. Examples of the viscosity controlling (meth) acrylic compound include benzyl methacrylate, cyclohexyl methacrylate, tetrahydropyranyl methacrylate, isobonyl (meth) acrylate, ethylhexyl acrylate, isooctyl acrylate, butyl acrylate (Meth) acrylic acid, trimethylolpropane formal monoacrylate, phenoxyethyl acrylate, tripropylene glycol diacrylate (meth) acrylate, ethyl acrylate, methyl acrylate, hydroxyl ethyl acrylate, acryloyloxypropionic acid, Propylene glycol diacrylate, propylene glycol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, trimethylol propane triacrylate, propoxylated glycerol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol Lauryl penta / hexyl acrylate and the like can be used. However, Not limited to. Depending on the type of substrate used in the bonding, a specific (meth) acrylic compound suitable for flowability can be selected and used.

In the whole composition, 1 to 30% by weight, preferably 5 to 20% by weight, of the (meth) acrylic compound for controlling viscosity can be used. Below this range, the viscosity control effect may be insignificant, and above this range, the physical properties of the entire composition may be affected.

(F) Additive

The radiation curable resin composition according to the present invention may further contain various additives as needed. The additive may be at least one selected from the group consisting of an antioxidant, a light stabilizer, an adhesion promoter, and a surfactant.

The adhesion promoting agent is a component having an action to improve adhesion with a substrate, and for example, a silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group or an epoxy group is preferable. Specific examples of the adhesion promoting agent include trimethoxysilylbenzoic acid,? -Methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane can be used as the silane coupling agent.

The surfactant is a component having an effect of improving coatability, coatability, uniformity and stain removal on a substrate, and may contain one or more selected from the group consisting of a fluorinated surfactant, a silicone surfactant and a nonionic surfactant Can be used in combination.

Representative examples that can be used as the antioxidant include Irganox 1010, Irganox 1035, Irganox 1076, and Irganox 1222 (Shiba Chemical Co., Ltd., Japan). Examples of the light stabilizer include Tinuvin 292, Tinuvin 144, Tinuvin 622LD (Shiba Gagai, Japan), sanol LS-770, sanol LS-765, sanol LS-292 and sanol LS-744 have.

In the whole composition, the additive may be varied according to the user's choice within a range not changing the physical properties required of the entire radiation-curable resin composition, and usually 0.01 to 5 wt%, preferably 0.05 to 3 wt%, may be used.

When the above-mentioned radiation curable composition is used for photo-curing, a cured film having a high transmittance can be produced with ease of adjustment of refractive index, less yellowing, and the like. The cured film may have a thickness of 1 to 5 mm.

In the case of the cured film made of the radiation curable composition described above, since the deep curing degree is very excellent, a sufficient adhesive force can be secured in a flexural appearance that may occur in a thickness of a module which becomes thinner. As a result, the durability against bending is improved, making it well suited for thin module joining. For example, in the case of a general module bonding material, in order to ensure durability, the thickness of the module bonding material is usually about 300 μm. In the case of the module bonding material formed by curing the radiation curable composition of the present invention, durability can be secured even with a thickness of 50-100 μm .

 Hereinafter, the present invention will be described in more detail with reference to the following examples. It is to be understood that the technical spirit of the present invention is not limited by the following examples.

Example

1. Synthesis of polymer resin (Production Examples 1 to 5)

Manufacturing example  1: Production of acrylic resin ( PA -One)

20 parts by weight of methyl methacrylate as a polymerization monomer, 10 parts by weight of butyl methacrylate, 20 parts by weight of dicyclopentyl methacrylate, 30 parts by weight of isobonyl methacrylate as a polymerization monomer, And 15 parts by weight of styrene was added thereto, followed by stirring at room temperature for 25 minutes. After stirring, 3 parts by weight of a thermal polymerization initiator V-65 (manufactured by Wako) and 2 parts by weight of dodecane thiol as a polymerization controlling agent were added. The internal temperature of the reaction solution was raised to 70 占 폚. After the temperature was elevated, the mixture was polymerized for 4 hours, and the reactor was cooled to 40 ° C to terminate the reaction. Thus, a polymer acrylic resin (PA-1) having a solid content of 100% and a weight average molecular weight of 25,000 was obtained.

Manufacturing example  2: Production of acrylic resin ( PA -2)

A polymeric acrylic resin (PA-2) having a solid content of 100% and a weight average molecular weight of 5,000 was obtained in the same manner as in Production Example 1, except that 10 parts by weight of styrene was used as a polymerization monomer and 7 parts by weight of a polymerization modifier dodecanethiol was added.

Manufacturing example  3: Urethane acrylate resin  Produce ( PUA -One)

A flask equipped with a mechanical stirrer, a thermometer and a cooling jacket was prepared, and 70 parts by weight of polypropylene glycol (Aldrich PPG2700) was added under nitrogen flow and heated to 40 캜 and stirred. 0.06 part by weight of dibutyltin dilaurate was added to the reaction solution, and the temperature of the reactor was raised to 65 캜. 20 parts by weight of isophorone diisocyanate was slowly added to this reaction solution. The reactants were measured by infrared spectrophotometer while reacting at 65 ° C to confirm the exhaustion state of the isocyanate group. When the exhaustion of the isocyanate group ceased, 10 parts by weight of 2-hydroxyethyl acrylate was slowly added to the reaction mixture. Again, the infrared spectrophotometer was measured to confirm the complete disappearance of the isocyanate group, and the reaction was terminated by lowering the reaction temperature to 40 ° C. To obtain a polymer urethane acrylic resin (PUA-1) having a solid content of 100% and a weight average molecular weight of 35,000.

Manufacturing example  4 : Urethane acrylate resin  Produce ( PUA -2)

(PUA-2) having a solid content of 100% and a weight average molecular weight of 8,000 was obtained in the same manner as in Production Example 3, except that 60 parts by weight of polymerized polypropylene glycol and 30 parts by weight of isophorone diisocyanate were used.

Manufacturing example  5: Polysiloxane  Resin Manufacturing ( PSi -One)

In a flask equipped with a stirrer and a thermometer, tetrahydrofuran (80 g) and ultrapure water (40 g) were placed as a solvent, potassium carbonate (0.4 g) as a catalyst was added, and the mixture was stirred at room temperature for 1 hour. Methyltrimethoxysilane (0.2 mol) was added to the reaction solution and reacted for 2 hours. (0.3 mol), trimethoxy (phenyl) silane (0.2 mol) and 3- (triethoxysilyl) propyl methacrylate (0.3 mol) ) Was slowly added dropwise over 30 minutes. After completion of the dropwise addition, the reaction was carried out for 8 hours. The polymer resin was extracted with methylene chloride, and the methylene chloride was distilled off under reduced pressure to obtain a polysiloxane resin (PSi-1) having a solid content of 100% and a weight average molecular weight of 15,000.

2. Synthesis of Photoinitiator (Preparation Example 6)

Manufacturing example  6: (E) - (1- hydroxycyclohexyl ) ( phenyl ) 메탄one  O- acetyl oxime Synthesis of PI -One)

Step 1: Synthesis of (E) - (1-hydroxycyclohexyl) (phenyl) methanone oxime

20 g of Irgacure 184 was added to 68 mL of ethanol and 11 mL of distilled water. Hydroxylamine hydrochloride (8.798 g) and sodium acetate (10.445 g) were added to the reaction. The reaction solution was circulatingly refluxed for 7 hours, and cold distilled water was added to form a precipitate. The resulting precipitate was filtered and washed with distilled water. The resulting white solid was washed with cold ethanol and dried to obtain a pale yellow solid having a yield of 74.5% of 16.0 g.

^{1 H-NMR (δ [ppm} ], DMSO- d 6): 1.49 ~ 1.53 (m, 6H), 1.90 (m, 4H), 2.0 (s, 1H-OH), 3.65 (s, 1H-OH), 7.52 (t, 3 H), 7.94 (dd, 2 H)

Step 2: Synthesis of (E) - (1-hydroxycyclohexyl) (phenyl) methanone O-acetyl oxime

(15.0 g), dichloromethane (90 mL) and triethylenamine (8.998 g) were added under nitrogen atmosphere, and acetyl chloride (6.94 g) was dissolved in dichloromethane Methane (5 mL) was slowly added to the solution. The internal temperature was raised to 10 DEG C, and the mixture was stirred for 3 hours. Acetonitrile (100 mL) and methylene chloride (100 mL) were added to the reaction mixture and the mixture was refluxed for 1 hour. The internal temperature was lowered to 0 캜, and 3 After standing for an hour, the solid was filtered to obtain a white solid (yield: 89.5%, 16g).

^{1 H-NMR (δ [ppm} ], CDCl 3): 1.48 ~ 1.53 (m, 6H), 1.90 (m, 4H), 2.28 (s, 3H), 3.65 (s, 1H-OH), 7.51 (t, 3H), < / RTI > 7.92 (dd, 2H)

3. Radiation curable resin compositions (Examples 1 to 45)

Example  1 to 10

60 parts by weight of the resin obtained in Production Examples 1 to 5, PA-1, PA-2, PUA-1, PUA-2 and PSi-1, 18 parts by weight of isobornyl acrylate, 12 parts by weight of propylene-2,2-diyl) bis ((allyloxy) benzene) and 5 parts by weight of trimethylolpropane triacrylate were used, and 5 parts by weight of PI-1 and Igacure 184 of Production Example 6 as photo- 1 to 10 were prepared.

Example  11 to 25

60 parts by weight of the resin obtained in Production Examples 1 to 5, PA-1, PA-2, PUA-1, PUA-2 and PSi-1, 18 parts by weight of isobornyl acrylate, 12 parts by weight of trimethylolpropane triacrylate and 5 parts by weight of trimethylolpropane triacrylate were used as a photoinitiator and 5 parts by weight of each of PI-1, Irgacure 184 and Irgacure 127 of Production Example 6 as photoinitiators were used to prepare the compositions of Examples 11 to 25.

Example  26 to 35

60 parts by weight of the resin obtained in Production Examples 1 to 5, PA-1, PA-2, PUA-1, PUA-2 and PSi-1, 18 parts by weight of isobornyl acrylate, 12 parts by weight of propylene-2,2-diyl) bis (2- (allyloxy) phenol) and 5 parts by weight of trimethylolpropane triacrylate were used, and 5 parts by weight of PI-1 and Irgacure 184 of Production Example 6 as photo- The compositions of Examples 26-35 were prepared.

Example  36 to 45

55 parts by weight of the resin obtained in Production Examples 1 to 5, PA-1, PA-2, PUA-1, PUA-2 and PSi-1, 18 parts by weight of isobornyl acrylate, 12 parts by weight of propane-2,2-diyl bis (2- (allyloxy) phenol), 5 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate) and 5 parts by weight of trimethylolpropane triacrylate The compositions of Examples 36 to 45 were prepared using 5 parts by weight of each of PI-1 and Irgacure 184 of Production Example 6 as photoinitiators.

The above embodiments are summarized in Tables 1 to 6.

Comparative Example  One

(Ultraviolet ray) curable resin composition (trade name: SVR1150) having a refractive index of 1.48 sold in the market was selected.

Comparative Example  2 to 6

60 parts by weight of the resin obtained in Production Examples 1 to 5, PA-1, PA-2, PUA-1, PUA-2 and PSi-1, 18 parts by weight of isobornyl acrylate, 12 parts by weight of trimethylolpropane triacrylate and 5 parts by weight of Irgacure TPO as a photoinitiator were used to prepare the compositions of Comparative Examples 2 to 6.

The following formula (7) shows the structures of the photoinitiators used in the comparative examples and the examples of the present invention.

(7)

The compositions of Comparative Examples 2 to 6 Comparative Example
2 Comparative Example
3 Comparative Example
4 Comparative Example
5 Comparative Example
6 PA-1 60 - - - - PA-2 - 60 - - - PUA-1 - - 60 - - PUA-2 - - - 60 - PSi-1 - - - - 60 Isobornyl acrylate 18 18 18 18 18 4-hydroxybutyl acrylate 12 12 12 12 12 4,4 '- (propane-2,2-diyl) bis ((allyloxy) benzene) - - - - - 4,4 '- (propane-2,2-diyl) bis (2- (allyloxy) phenol) - - - - - Pentaerythritol tetrakis (3-mercaptopropionate) - - - - - Trimethylolpropane triacrylate 5 5 5 5 5 PI-1 - - - - - Irgacure 184 - - - - - Irgacure TPO 5 5 5 5 5 Irgacure 127 - - - - -

The compositions of Examples 1 to 10 Example
One Example
2 Example
3 Example
4 Example
5 Example
6 Example
7 Example
8 Example
9 Example
10 PA-1 60 - - - - 60 - - - - PA-2 - 60 - - - - 60 - - - PUA-1 - - 60 - - - - 60 - - PUA-2 - - - 60 - - - - 60 - PSi-1 - - - - 60 - - - - 60 Isobornyl acrylate 18 18 18 18 18 18 18 18 18 18 4-hydroxybutyl acrylate - - - - - - - - - - 4,4 '- (propane-2,2-diyl) bis ((allyloxy) benzene) 12 12 12 12 12 12 12 12 12 12 4,4 '- (propane-2,2-diyl) bis (2- (allyloxy) phenol) - - - - - - - - - - Pentaerythritol tetrakis (3-mercaptopropionate) - - - - - - - - - - Trimethylolpropane triacrylate 5 5 5 5 5 5 5 5 5 5 PI-1 5 5 5 5 5 - - - - - Irgacure 184 - - - - - 5 5 5 5 5 Irgacure TPO - - - - - - - - - - Irgacure 127 - - - - - - - - - -

The compositions of Examples 11 to 20 Example
11 Example
12 Example
13 Example
14 Example
15 Example
16 Example
17 Example
18 Example
19 Example
20 PA-1 60 - - - - 60 - - - - PA-2 - 60 - - - - 60 - - - PUA-1 - - 60 - - - - 60 - - PUA-2 - - - 60 - - - - 60 - PSi-1 - - - - 60 - - - - 60 Isobornyl acrylate 18 18 18 18 18 18 18 18 18 18 4-hydroxybutyl acrylate 12 12 12 12 12 12 12 12 12 12 4,4 '- (propane-2,2-diyl) bis ((allyloxy) benzene) - - - - - - - - - - 4,4 '- (propane-2,2-diyl) bis (2- (allyloxy) phenol) - - - - - - - - - - Pentaerythritol tetrakis (3-mercaptopropionate) - - - - - - - - - - Trimethylolpropane triacrylate 5 5 5 5 5 5 5 5 5 5 PI-1 5 5 5 5 5 - - - - - Irgacure 184 - - - - - 5 5 5 5 5 Irgacure TPO - - - - - - - - - - Irgacure 127 - - - - - - - - - -

The compositions of Examples 21 to 25 Example 21 Example
22 Example
23 Example
24 Example
25 PA-1 60 - - - - PA-2 - 60 - - - PUA-1 - - 60 - - PUA-2 - - - 60 - PSi-1 - - - - 60 Isobornyl acrylate 18 18 18 18 18 4-hydroxybutyl acrylate 12 12 12 12 12 4,4 '- (propane-2,2-diyl) bis ((allyloxy) benzene) - - - - - 4,4 '- (propane-2,2-diyl) bis (2- (allyloxy) phenol) - - - - - Pentaerythritol tetrakis (3-mercaptopropionate) - - - - - Trimethylolpropane triacrylate 5 5 5 5 5 PI-1 - - - - - Irgacure 184 - - - - - Irgacure TPO - - - - - Irgacure 127 5 5 5 5 5

The compositions of Examples 26 to 35 Example
26 Example
27 Example
28 Example
29 Example
30 Example
31 Example
32 Example
33 Example
34 Example
35 PA-1 60 - - - - 60 - - - - PA-2 - 60 - - - - 60 - - - PUA-1 - - 60 - - - - 60 - - PUA-2 - - - 60 - - - - 60 - PSi-1 - - - - 60 - - - - 60 Isobornyl acrylate 18 18 18 18 18 18 18 18 18 18 4-hydroxybutyl acrylate - - - - - - - - - - 4,4 '- (propane-2,2-diyl) bis ((allyloxy) benzene) - - - - - - - - - - 4,4 '- (propane-2,2-diyl) bis (2- (allyloxy) phenol) 12 12 12 12 12 12 12 12 12 12 Pentaerythritol tetrakis (3-mercaptopropionate) - - - - - - - - - - Trimethylolpropane triacrylate 5 5 5 5 5 5 5 5 5 5 PI-1 5 5 5 5 5 - - - - - Irgacure 184 - - - - - 5 5 5 5 5 Irgacure TPO - - - - - - - - - - Irgacure 127 - - - - - - - - - -

The compositions of Examples 36 to 45 Example
36 Example
37 Example
38 Example
39 Example
40 Example
41 Example
42 Example
43 Example
44 Example
45 PA-1 55 - - - - 55 - - - - PA-2 - 55 - - - - 55 - - - PUA-1 - - 55 - - - - 55 - - PUA-2 - - - 55 - - - - 55 - PSi-1 - - - - 55 - - - - 55 Isobornyl acrylate 18 18 18 18 18 18 18 18 18 18 4-hydroxybutyl acrylate - - - - - - - - - - 4,4 '- (propane-2,2-diyl) bis ((allyloxy) benzene) - - - - - - - - - - 4,4 '- (propane-2,2-diyl) bis (2- (allyloxy) phenol) 12 12 12 12 12 12 12 12 12 12 Pentaerythritol tetrakis (3-mercaptopropionate) 5 5 5 5 5 5 5 5 5 5 Trimethylolpropane triacrylate 5 5 5 5 5 5 5 5 5 5 PI-1 5 5 5 5 5 - - - - - Irgacure184 - - - - - 5 5 5 5 5

Experimental Example  : Measurement of hardening rate

In order to effectively bond two modules or two substrates using a radiation curable resin composition, it is desirable to realize a fast curing rate. For fast curing speed, it is desirable that the C = C bond in the acrylate group of the resin composition is rapidly converted to the C-C bond by ultraviolet irradiation.

The curing rate can be evaluated by measuring the amount of heat generated when the C = C bond is converted to the C-C bond using DSC (Differential Scanning Calorimetry). A certain amount of the composition is placed in a DSC cell, exposure is divided, exposure is carried out from 25 ° C to 250 ° C at a rate of 5 ° C / min, and then the area of the exothermic peak is calculated and the calorific value is measured. The calculation formula is as follows.

Curing rate (%) = (calorific value of non-exposed sample - calorific value of exposed sample) / calorific value of unexposed sample × 100

Experimental Example  : Shear stress  Measure

Shear stress was measured according to ASTM D1002 using a universal testing machine (UTM). A coating space was made to have a width of 6 mm on one end of a 3 mm glass with a thickness of 0.3 mm and a resin composition was applied. The same glass as above was then placed on the coated composition and exposed to prepare a specimen. The shear stress was measured at a shear load of 100 kN and a speed of 50 mm / min after exposure.

Experimental Example  : Adhesive strength measurement

The adhesive strength was measured using a UTM. The resin composition was coated on a glass of 25 mm × 70 mm × 3 mm with a width of 6 mm with a 0.3 mm tape. The glass composition of the same size was overlaid on each other, . After fixing the upper glass, pressing both sides of the lower glass at a speed of 50 mm / min, the maximum force when the adhesive surface fell was measured.

Experimental Example  : Elongation  Measure

The elongation was measured using a UTM, and the sample was exposed with a size of 4 mm × 60 mm × 4 mm. The sample was exposed to 40 mm and then stretched at a rate of 50 mm / min to measure the elongation at breakage .

Experimental Example  : Refractive index and Optical property

ASTM D1003, Yellow Index (ASTM D1925) and Haze (ASTM D1925) were measured using a spectrophotometer, and the refractive index was measured using a ABBE Refractometer. D1003) were measured.

Experimental Example  : Deep hardening degree  Measure

The depth of hardening is a measure of the hardening penetration rate of the unexposed portion. To measure the depth of hardening, specimens were prepared on a 10 mm × 60 mm × 3 mm glass with a 0.3 mm tape and a width of 6 mm. At this time, the upper part was coated with the resin composition without applying the tape, covered with the same glass, and then the two glass pieces were fixed with a jig. 30 minutes after the specimen was exposed and exposed, the upper glass was peeled off and the depth of the cured resin composition was measured to compare the degree of curing.

As the exposure conditions in the above-mentioned experimental examples, a lamp having a wavelength of 385 nm of LED was used as a light source and exposed at 250 mJ / cm ² . Also, the characteristics of the above embodiments were compared with Comparative Examples 1 to 6.

Curing Rate and Physical Properties of Comparative Examples 1 to 6 and Examples 1 to 25 division Hardening rate
(%) Shear stress
(gf / mm ² ) Adhesive strength
(MPa) Elongation (%) Yellow index Haze Permeability
(%) Comparative Example 1 92 102 0.98 200 0.60 0.85 98 Comparative Example 2 75 Not measurable Not measurable Not measurable 0.54 0.26 99 Comparative Example 3 74 Not measurable Not measurable Not measurable 0.46 0.25 98 Comparative Example 4 76 Not measurable Not measurable Not measurable 0.43 0.23 98 Comparative Example 5 75 Not measurable Not measurable Not measurable 0.52 0.21 99 Comparative Example 6 70 Not measurable Not measurable Not measurable 0.43 0.22 99 Example 1 94 135 1.82 360 0.42 0.36 99 Example 2 92 142 1.64 330 0.41 0.54 99 Example 3 96 165 1.98 600 0.55 0.42 99 Example 4 96 172 1.89 300 0.62 0.62 98 Example 5 94 165 1.75 400 0.63 0.15 98 Example 6 92 127 1.32 250 0.25 0.42 98 Example 7 91 134 1.06 200 0.35 0.35 98 Example 8 94 145 1.45 600 0.34 0.66 98 Example 9 93 153 1.63 300 0.54 0.54 99 Example 10 89 112 0.88 450 0.16 0.25 99 Example 11 92 135 0.92 350 0.65 0.26 98 Example 12 91 142 0.85 200 0.49 0.25 98 Example 13 96 165 1.52 850 0.85 0.24 99 Example 14 95 166 1.49 350 0.42 0.35 99 Example 15 91 134 1.23 550 0.65 0.15 99 Example 16 90 124 0.74 180 0.43 0.24 98 Example 17 87 106 0.65 230 0.61 0.28 98 Example 18 93 132 1.23 900 0.25 0.29 98 Example 19 92 115 1.05 450 0.64 0.31 99 Example 20 89 112 1.11 600 0.72 0.21 99 Example 21 85 114 1.01 140 0.62 0.23 98 Example 22 84 121 0.85 160 0.35 0.15 98 Example 23 88 125 1.34 600 0.45 0.19 98 Example 24 87 134 1.25 240 0.62 0.54 98 Example 25 82 108 1.06 200 0.52 0.42 99

Curing Rate and Physical Properties of Examples 26 to 45 division Hardening rate
(%) Shear stress
(gf / mm ² ) Adhesive strength
(MPa) Elongation (%) Yellow index Haze Permeability
(%) Example 26 96 175 1.75 300 0.75 0.33 98 Example 27 95 185 1.64 150 0.68 0.26 99 Example 28 98 202 2.54 600 0.45 0.24 98 Example 29 98 233 2.73 300 0.48 0.35 99 Example 30 95 156 1.86 350 0.66 0.61 99 Example 31 96 145 1.45 360 0.52 0.65 98 Example 32 95 165 1.25 320 0.43 0.25 98 Example 33 96 188 1.84 640 0.52 0.51 98 Example 34 95 192 1.62 350 0.53 0.45 98 Example 35 94 145 1.35 420 0.64 0.63 98 Example 36 98 184 2.56 200 0.58 0.24 99 Example 37 98 194 2.22 150 0.59 0.25 99 Example 38 99 254 2.85 550 0.52 0.33 98 Example 39 100 270 2.45 300 0.48 0.32 98 Example 40 98 185 2.12 450 0.46 0.51 98 Example 41 96 165 1.78 280 0.45 0.42 98 Example 42 95 174 1.42 190 0.43 0.53 99 Example 43 96 182 1.85 640 0.25 0.42 98 Example 44 96 194 1.64 380 0.26 0.62 98 Example 45 95 146 1.54 490 0.45 0.21 98

The refractive index and depth of cure (compositions having a curing rate of 95% or more) of Examples and Comparative Examples division Hardening rate
(%) Deep hardening degree
(mm) Refractive index Example 3 96 2.2 1.56 Example 4 96 2.3 1.54 Example 13 96 2.6 1.48 Example 14 95 2.4 1.46 Example 26 96 3.2 1.52 Example 27 95 3.3 1.51 Example 28 98 3.6 1.58 Example 29 98 3.8 1.56 Example 30 95 2.8 1.55 Example 31 96 2.8 1.52 Example 32 95 2.8 1.51 Example 33 96 3.1 1.58 Example 34 95 3.2 1.56 Example 35 94 2.5 1.55 Example 36 98 4.1 1.58 Example 37 98 4.3 1.56 Example 38 99 4.8 1.64 Example 39 100 4.8 1.62 Example 40 98 3.9 1.61 Example 41 96 3.5 1.58 Example 42 95 3.4 1.56 Example 43 96 3.7 1.64 Example 44 96 3.9 1.62 Example 45 95 3.2 1.56 Comparative Example 1 92 1.2 1.48

As shown in the above results, the basic optical characteristics of the compositions of the Examples were all satisfactory, but the curing rate at 250 mJ / cm ² was different depending on the type of photoinitiator. In the case of Irgacure TPO, which is a photo initiator without an OH group, the degree of curing was very low. The oxime ester type photopolymerization initiator of Production Example 6 showed faster curing rate than Irgacure 184 and Irgacure 127, which are general ketone type photoinitiators.

And 4,4 '- (propane-2,2-diyl) bis ((allyloxy) benzene) which is a hydrogen donor-free 4,4' - 2,2-diyl) bis (2- (allyloxy) phenol) was used.

Also, radiation curable resin compositions capable of controlling the refractive index from 1.46 to 1.64 can be obtained when pentaerythritol tetrakis (3-mercaptopropionate), which may be present in the cured film due to radical light reaction during curing, is added I could.

Claims (12)

(A) 20 to 80% by weight of a polymer resin;
(Meth) acrylate, bisphenol acrylate, bisphenol epoxy acrylate, fluorene acrylate, urethane acrylate, bromine (B), and the like. And 5 to 70% by weight of at least one unsaturated compound for controlling refractive index selected from the group consisting of acrylate including sulfur;
(C) 0.5-10% by weight of an oxime ester-based photoinitiator containing a hydrogen donor in which a hydrogen donor is present at the alpha carbon position of the C = N bond of the oxime ester-based photoinitiator;
(Meth) acrylate, 4-hydroxybutyl (meth) acrylate, polypropylene glycol (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, mono (meth) acrylate, mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, N-hydroxyethyl But are not limited to, acrylic acid, crotonic acid,? -Methyl crotonic acid,? -Ethyl crotonic acid, isocrotonic acid, thylacetic acid, angelic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, Bis ((allyloxy) benzene), 4,4 '- (propane-2,2'-diyl) bis (2- 1 to 40% by weight of at least one hydrogen donor-containing (meth) acrylic compound selected from the group consisting of And
(E) benzyl methacrylate, cyclohexyl methacrylate, tetrahydropyranyl methacrylate, isobonyl (meth) acrylate, ethylhexyl acrylate, isooctyl acrylate, butyl acrylate, ethyl acrylate, (Meth) acrylic acid, trimethylol propane formal monoacrylate, phenoxy ethyl acrylate, tripropylene glycol diacrylate, hexanediol diacrylate, diethyleneglycol diacrylate, diethyleneglycol diacrylate, Acrylate, neopentyl glycol diacrylate, trimethylol propane triacrylate, propoxylated glycerol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol penta / hexaacrylate. (Meth) acrylate (meth) acrylate 1 to 30% by weight,
Wherein the hydrogen donor is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an amine group and a thiol group. The method according to claim 1,
Wherein the unsaturated compound for controlling refractive index is a monomer or oligomer containing an ethylenic unsaturated group. The method according to claim 1,
The unsaturated compound for controlling refractive index is a (meth) acrylic monomer. The method according to claim 1,
Wherein the polymer resin is a polyimide or polysiloxane including a (meth) acrylate copolymer, polyisoprene, polybutadiene, polyurethane, polyester, polyimide, polyamic acid, and sulfur. The method according to claim 1,
Wherein the hydrogen donor-containing photoinitiator is at least one selected from the following general formulas (1) and (2):
[Chemical Formula 1]

(2)

In the above formula (1) or (2), Hy represents -OH, -COOH, -NH ₂ Or -SH,
X is -CR'R "-, -O-, -S- or -Se-, R 'and R" are each independently hydrogen or methyl,
R ₁ to R ₈ are each independently selected from the group consisting of hydrogen, halogen, amino, nitro, cyano, hydroxy, substituted or unsubstituted C ₁ -C ₃₀ alkyl, substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl, unsubstituted C ₁ -C ₃₀ alkoxy, substituted or unsubstituted C ₆ -C ₃₀ aryl, substituted or unsubstituted C ₆ -C ₃₀ aralkyl (aralkyl), substituted or unsubstituted C ₁ -C ₃₀ heteroalkyl , Substituted or unsubstituted C ₂ -C ₃₀ heterocycloalkyl, substituted or unsubstituted C ₅ -C ₃₀ heteroaryl, substituted or unsubstituted C ₅ -C ₃₀ heteroaralkyl, and adjacent substituents are linked to form a C ₅ -C ₁₀ A ring can be formed. 6. The method of claim 5,
And Hy is -OH. The method according to claim 1,
(F) at least one additive selected from the group consisting of an antioxidant, a light stabilizer, an adhesion promoting agent, and a surfactant. (A) 20 to 80% by weight of a polymer resin;
(Meth) acrylate, bisphenol acrylate, bisphenol epoxy acrylate, fluorene acrylate, urethane acrylate, bromine (B), and the like. And 5 to 70% by weight of at least one unsaturated compound for controlling refractive index selected from the group consisting of acrylate including sulfur;
(C) 0.5 to 10% by weight of a hydrogen donor-containing photoinitiator selected from the following formula (5);
(Meth) acrylate, 4-hydroxybutyl (meth) acrylate, polypropylene glycol (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, mono (meth) acrylate, mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, N-hydroxyethyl But are not limited to, acrylic acid, crotonic acid,? -Methyl crotonic acid,? -Ethyl crotonic acid, isocrotonic acid, thylacetic acid, angelic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, Bis ((allyloxy) benzene), 4,4 '- (propane-2,2'-diyl) bis (2- 1 to 40% by weight of at least one hydrogen donor-containing (meth) acrylic compound selected from the group consisting of And
(E) benzyl methacrylate, cyclohexyl methacrylate, tetrahydropyranyl methacrylate, isobonyl (meth) acrylate, ethylhexyl acrylate, isooctyl acrylate, butyl acrylate, ethyl acrylate, (Meth) acrylic acid, trimethylolpropane formal monoacrylate, phenoxyethyl acrylate, tripropylene glycol diacrylate, hexanediol diacrylate, hexanediol diacrylate, Acrylate, neopentyl glycol diacrylate, trimethylol propane triacrylate, propoxylated glycerol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol penta / hexaacrylate. (Meth) acrylate (meth) acrylate Radiation-curing resin containing the water of 1 to 30% by weight of the composition:
[Chemical Formula 5]

9. The method of claim 8,
Wherein the unsaturated compound for controlling refractive index is a (meth) acrylic monomer containing an ethylenic unsaturated group. 10. The method of claim 9,
Wherein the unsaturated compound for controlling refractive index is an acrylate containing sulfur. A cured film produced by curing a radiation curable resin composition according to any one of claims 1 to 10 by direct bonding between a touch panel and a display body. 12. The method of claim 11,
Wherein the cured film has a refractive index of 1.45 to 1.65 and a thickness of 1 to 5 mm.