KR101251457B1 - Acryl acrylate and resin composition including the same - Google Patents

Abstract

An acrylic acrylate compound and a resin composition comprising the same are disclosed. The acryl acrylate compound is a reaction compound formed by reacting a reaction catalyst with at least one of a methyl acrylate compound, an ethyl acrylate compound and a butyl acrylate compound using a monomer having at least one acrylate group and a methacrylate group as a solvent. to be. The resin composition comprises about 30 to 70 wt% of the acrylic acrylate compound, about 20 to 60 wt% of the reactive monomer comprising at least one vinyl group, acrylate group or methacrylate group, about 0.1 to 15 wt% of urethane Acrylate and about 0.5 to 10 weight percent photopolymerization initiator. Excellent adhesion and wear resistance to PMMA.

Description

ACRYL ACRYLATE AND RESIN COMPOSITION INCLUDING THE SAME}

The present invention relates to an acrylic acrylate compound and a resin composition comprising the same, and more particularly, to an acrylic acrylate compound applicable to a film of a light guide plate (LGP) and a polymethyl methacrylate of the light guide plate, including the same. The photocurable resin composition excellent in the adhesive force to a raw material.

A film is formed on the PMMA material of the light guide plate using resin. PMMA is used as a raw material for various optical parts because of its high light transmittance in the visible light range, small birefringence and excellent light resistance. On the surface of such a PMMA material, a resin film is formed to improve physical properties.

Conventionally used acrylate resin has a limitation that it is difficult to use because of low adhesion. Epoxy urethane acrylate compounds that are generally used can increase the wear resistance but has the disadvantage of low adhesion. In the case of epoxy acrylate, the yellowing of the film is severe after curing, and the yellowing degrades the performance of the film and, in severe cases, also affects the color of the display device. Therefore, there is a need for a film for PMMA material having high adhesion and wear resistance without yellowing.

An object of the present invention is to solve the above problems, to provide an acrylic acrylate compound that can be applied to a resin composition having excellent wear resistance and excellent adhesion to the PMMA substrate in place of conventional epoxy acrylate and urethane acrylate. .

Another object of the present invention is to provide a photocurable resin composition comprising the acrylic acrylate and excellent adhesion to the PMMA material of LGP.

Still another object of the present invention is to provide a method of manufacturing a light guide plate capable of forming a film having excellent adhesion and wear resistance on a PMMA material.

In order to achieve the above object, the present invention uses a monomer comprising at least one acrylate group or a methacrylate group as a solvent, and at least one of a methyl acrylate compound, an ethyl acrylate compound, and a butyl acrylate compound with a reaction catalyst. It provides an acrylic acrylate compound formed by the reaction.

In one embodiment, the reaction catalyst is to use at least one compound selected from the group consisting of azobisisobutyronitrile, azobis isopentironitrile and azobis methylpropion amidine.

In order to achieve the above object of the present invention, at least one of a methyl acrylate compound, an ethyl acrylate compound and a butyl acrylate compound and azobis using a monomer including at least one acrylate group and a methacrylate group as a solvent. 30 to 70 wt% of an acrylic acrylate compound obtained by polymerizing at least one reaction catalyst selected from the group consisting of isobutyronitrile, azobis isopentironitrile, and azobis methylpropion amidine; Photocurable with PMMA adhesion comprising 20 to 60% by weight reactive monomer comprising at least one vinyl, acrylate or methacrylate group, 0.1 to 15% by weight urethane acrylate and 0.5 to 10% by weight photopolymerization initiator It provides a resin composition.

In one embodiment, the reactive monomers are acryloyl morpholine, benzyl acrylate, cyclohexyl acrylate, phenoxy ethyl acrylate, phenoxy diethylene glycol acrylate, phenoxy tetraethylene glycol acrylate, phenoxy hexa Ethylene glycol acrylate, dicyclo pentadiene acrylate, ortho phenylphenoxy ethyl acrylate, 4-hydroxy butyl acrylate, cyclohexane di methanol mono acrylate, neopentyl acrylate, tripropylene glycol diacrylate, polyethylene Glycol diacrylate, tris (2-hydroxyethyl) isocyanurate diacrylate, dimethylol tricyclodecane diacrylate, ethylene oxide addition type bisphenol A diacrylate, ethylene oxide 3 mole addition type trimethylol propane triacrylate , Ethylene oxide 6 molar addition type trimethylol propane triacrylate, pentaerythritol triacrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexa acrylate and caprolactone modified dipentaerythritol hexa acryl At least one compound selected from the group consisting of rates is used.

In one embodiment, the urethane acrylate is at least one compound selected from the group consisting of polycarbonate urethane modified acrylate, polyether urethane modified acrylate, polyester urethane modified acrylate and polycaprolactone urethane modified acrylate Do it.

In one embodiment, the photopolymerization initiator is benzophenone and its derivatives, benzoin, benzoin alkyl ether benzyl dimethyl ketal, 1-hydroxy cyclohexyl phenyl ketone, diethoxy acetophenone, phosphine oxide type, amino acetophenone type At least one selected from the group consisting of 2-hydroxy-2-methyl-1-phenylpropano-1-non and 2-benzyl-2-dimethylamide-1- (4-morpholinaphenyl) -butanane Use compound.

Another object of the present invention described above is achieved by a method of manufacturing a light guide plate comprising the step of coating the resin composition on a PMMA material and the step of photocuring the resin composition to form a film.

The acrylic acrylate compound according to the present invention can be used for optical products, ie, optical lenses, optical films and optical media. In particular, the optical film may be used in a display product such as a liquid crystal display or a plasma display panel, and in particular, may improve physical properties of the light guide plate disposed on the rear surface of the liquid crystal display panel. The resin composition containing the said acryl acrylate compound is especially excellent in the adhesive force with respect to PMMA material of a light-guide plate, and its abrasion resistance is good.

Hereinafter, the acrylic acrylate compound and the resin composition including the same according to the embodiment of the present invention will be described in detail. While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It is to be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but on the contrary, is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "having" are intended to indicate that there is a feature, step, component, or combination thereof described in the specification, and one or more other features, steps, components or It should be understood that they do not preclude the presence or possibility of adding these in advance.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in the commonly used dictionaries should be construed as having meanings consistent with the meanings in the context of the related art and shall not be construed in ideal or excessively formal meanings unless expressly defined in this application. Do not.

Hereinafter, the present invention will be described in more detail.

First, the acryl acrylate compound which concerns on this invention is demonstrated.

The acryl acrylate compound having adhesion to the PMMA of the present invention is a compound having an acrylate group at the terminal of the structure mainly having a methyl group, an ethyl group or a butyl group, and at least one of a methyl acrylate compound, an ethyl acrylate compound and a butyl acrylate compound. It is prepared using one acrylate. The acrylate compound is combined in the presence of a reaction catalyst to produce an acrylic acrylate compound. As the reaction solvent, a monomer containing at least one acrylate group and a methacrylate group is used. Eventually, when the methyl, ethyl and / or butyl acrylate compound reacts to form a solid acryl acrylate compound in the presence of a catalyst, a monomer compound having an acrylate group or a methacrylate group acts as a solvent for the solid acrylate compound. It is to provide an acryl acrylate compound in solution. The monomer including an acrylate group and a methacrylate group used as a solvent is a monomer prepared by reacting an acid with an alcohol, and does not participate in the reaction, and serves to dissolve the solid acrylate reaction compound.

As the reaction catalyst of the photocurable resin composition, at least one compound of azobisisobutyronitrile, azobis isopentironitrile, and azobis methylpropion amidine is used. Its amount is to be in the range of about 0.01 to 1.0% by weight based on the total amount of reactants. Here, the total amount of the reactants means an amount in which at least one of a methyl acrylate compound, an ethyl acrylate compound, and a butyl acrylate compound is combined with a reaction catalyst.

The manufacturing method of the above-mentioned acryl acrylate compound is as follows.

First, a proper amount of a compound having at least one of an acrylate group or a methacrylate group is added to the reaction vessel as an acrylate monomer to be used as a solvent. Since the acrylate monomer is used as a solvent, an appropriate amount may be used in consideration of the dilution force of the solvent and the like. Preferably, the acrylate monomer is in a range of about 20 to 50 wt% based on the total amount of the reactants.

Thereafter, the appropriate amount of methyl acrylate, ethyl acrylate and / or butyl acrylate compound and catalyst are slowly added while stirring the solvent. For example, 1 equivalent of methyl acrylate, 0.5 equivalent of ethyl acrylate, 0.5 equivalent of butyl acrylate and the catalyst are sequentially added dropwise to the reactor and maintained at about 90 ° C. with stirring.

When the dropping of the raw material is completed and the reaction is stabilized, the reaction is allowed to proceed slowly while maintaining for 2 hours, and then cooled to about 70 ° C., filtered to prepare an acrylic acrylate compound, and then packaged.

The photocurable resin composition which has adhesiveness to PMMA of this invention is an acryl acrylate compound mentioned above; Reactive monomer containing at least one of a vinyl group, an acrylate group, and a methacrylate group in a molecule | numerator; Urethane acrylate and photopolymerization initiator.

An acryl acrylate compound is a component which gives the outstanding adhesive force with respect to a base material, and is especially a component excellent in adhesiveness with respect to PMMA. Based on the total amount of the composition of the acrylic acrylate compound used, the amount was in the range of about 30 to 70% by weight. If the amount thereof is less than about 30% by weight, the adhesion is deteriorated, and if the amount thereof is more than about 70% by weight, the wear resistance is lowered, which is not preferable. More preferably used in the range of about 40 to 60% by weight.

Reactive monomer is a monomer having a function of excellent adhesion to the material as a monomer having a monofunctional group, such as acryloyl morpholine, benzyl acrylate, dicyclopentadiene acrylate, cyclohexyl acrylate, phenoxy ethyl acrylate, phenoxy Diethylene glycol acrylate, phenoxy tetraethylene glycol acrylate, phenoxy hexaethylene glycol acrylate, ortho phenylphenoxy ethyl acrylate, 4-hydroxy butyl acrylate and cyclohexane dimethanol monoacrylate and the like are available Neopentyl acrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, tris (2-hydroxyethyl) isocyanurate diacrylate, dimethylol tricyclodecane diacryl Ethylene Oxa Dye addition type bisphenol A diacrylate etc. can be used, As a monomer which has a trifunctional or more than trifunctional group, Ethylene oxide 3 mol addition type trimethylol propane triacrylate, Ethylene oxide 6 mol addition type trimethylol propane triacrylate, pentaerythritol triacrylate , Tris (acryloxyoxy) isocyanate, dipentaerythritol hexa acrylate, caprolactone modified dipentaerythritol hexa acrylate, and the like can be used.

The amount of reactive acrylate monomer is in the range of about 20 to 60% by weight based on the total amount of the composition. If the amount thereof is less than about 20% by weight, the workability is lowered as the shop degree increases, and if the amount thereof is more than about 60% by weight, the curability is lowered, which is not preferable. More preferably in the range of about 30 to 50% by weight.

The urethane acrylate is a component having a function of excellent wear resistance, polycarbonate urethane modified acrylate, polyether urethane modified acrylate, polyester urethane modified acrylate, polycaprolactone urethane modified acrylate and the like can be used. Its usage amount is in the range of about 0.1 to 15% by weight, based on the total amount of the composition. If the amount thereof is less than about 0.1% by weight, the wear resistance is lowered, which is undesirable. If the amount thereof is more than about 15% by weight, the adhesion to the material is lowered, which is not preferable.

Examples of the photopolymerization initiator include benzophenone and its derivatives, benzoin, benzoin alkyl ether benzyl dimethyl ketal, 1-hydroxy cyclohexyl phenyl ketone, diethoxy acetophenone, phosphine oxide, amino acetophenone and 2-hydroxy 2-methyl-1-phenylpropano-1-non, 2-benzyl-2-dimethylamide-1- (4-morpholinaphenyl) -butanane, and the like can be used.

Its use amount is in the range of about 0.5 to 10% by weight, preferably about 1 to 5% by weight, based on the total amount of the composition.

By applying the above-mentioned resin composition on a PMMA material and photocuring to form a coating layer, it is possible to manufacture an optical film having adhesion to PMMA, and the optical film can be formed to have a predetermined pattern as necessary.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments.

<Production of Acrylic Acrylate Compound>

The acrylic acrylate compound was prepared as follows.

&Lt; Example 1 >

223 g of phenoxy acrylate was added to a four-necked flask, and while stirring, 130 g of methyl acrylate, 91 g of butyl acrylate, and 2 g of azobisisobutyronitrile were slowly added dropwise with a catalyst to raise the temperature to 90 ° C. It was kept for 2 hours when the temperature became constant. After the reaction was completed, 446 g of an acrylic acrylate polymerization product in a clear liquid state was obtained.

<Example 2>

206 g of phenoxy acrylate was added to a four-necked flask, and while stirring, 130 g of methyl acrylate, 74 g of ethyl acrylate, and 2 g of azobisisobutyronitrile were slowly added dropwise with a catalyst to raise the temperature to 90 ° C. It was kept for 2 hours when the temperature became constant. After the reaction was completed, 412 g of an acrylic acrylate polymerization product in a clear liquid state was obtained.

<Production of Photocurable Resin Composition>

Next, the photocurable resin composition was manufactured using the acryl acrylate compound obtained through Examples 1 and 2 mentioned above.

<Examples 3 and 4>

A photocurable resin composition was prepared by mixing reactive acrylate monomers, urethane acrylates, and photopolymerization initiators with the acrylic acrylate compounds prepared in Examples 1 and 2, respectively. Specific components and the amount thereof used are shown in Table 1.

Table 1 shows the acrylic acrylates prepared in Examples 1 and 2 as Sample-A and Sample-B, respectively, and the resin compositions for LGP of other companies to be compared as Sample-C and Sample-D, respectively, and reactive monomers and photopolymerization, respectively. The sample compounding ratio which added the initiator is shown.

TABLE 1

Note 1 UBC urethane acrylate (manufactured by Cytec Corporation)

2) Reactive acrylate or vinyl monomer

(Note 3) Photoinitiator: 2-hydroxy-2-methyl-1-phenylpropa-1-non

<Manufacture of LGP>

The photocurable resin composition prepared according to Examples 3 and 4 was irradiated with ultraviolet rays toward the PMMA film in contact with the coating surface of the PMMA film, which is a material of LGP, to photocure the composition coated on the frame, and adhered to the PMMA to cure. The separated coating layer was separated to prepare a LGP having a dot pattern layer formed on one surface of the PMMA film.

<Characteristics of UV Coating Composition>

Some characteristics of the resin compositions according to Examples 3 and 4 and Comparative Examples 1 and 2 were examined.

Table 2 discloses the results of evaluating the physical properties after curing the samples of Table 1 with an ultraviolet lamp. For reference, the test method for obtaining each physical property data shown in Table 2 is as follows.

First, the curability was calculated for the energy required to cure the resin composition on a 200 x 200 mm PMMA sheet with a thickness of about 20 microns and then cure with an ultraviolet curing device of a high pressure mercury lamp of 120 W.

The pencil hardness is flattened with the tip of the pencil tip to sand paper 400 and the edge is sharpened. The pencil hardness is inclined 45 degrees, and the 1Kg load is applied to the test surface, and the position of the scratch about 20 mm in length at the speed of about 3 mm / sec in the direction of the pencil core. 5 times while varying, the graphite of the pencil attached to the test surface was wiped off with a rubber eraser or gauze to examine the groove state of the test surface. In this case, starting from a soft pencil five times, there should be no scratches more than three times, the length of implementation is about 30mm and 10mm from the start of each line was excluded from the judgment. The pencil hardness increases gradually in the order of 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H and 6H.

Adhesion is on the coated surface of PMMA film with 1.5mm of horizontal line and 11 lines of horizontal lines to make 100 cells, and then attach 3M cellophane tape No. 600 and remove it immediately. Was tested by counting (ASTM D3359).

Abrasion resistance was performed using a Taber abraser manufactured by Taber. Abrasion wheels were loaded with 1 kg of weight and rotated 50 cycles to determine the amount of wear by measuring the reduced weight (mg). The lower the number, the smaller the weight, and the lower the wear resistance.

<Table 2>

As described in Table 2, the resin composition prepared using the acrylic acrylate compound (Sample-A and Sample-B) according to the present invention is compared with the properties of the comparative resin composition (Sample-C and Sample-D). Although, curability, pencil hardness, etc. are similar with respect to an Example and a comparative example, it can confirm that the acryl acrylate which concerns on this invention shows the outstanding characteristic in terms of adhesiveness and abrasion resistance.

As described above, the acrylic acrylate and the photocurable resin composition of the present invention are superior in adhesion to the substrate of LGP and have excellent abrasion resistance than the conventional ones.

As described above, the composition using the acrylic acrylate resin according to the present invention has excellent adhesion to the substrate and excellent abrasion resistance than the conventional acrylate resin composition, so that the industrial optical lens used in optical films, cameras, copiers, printers, etc. It may be used in optical lenses and other optical materials for eyeglass materials.

In addition, the LGP manufactured using the photocurable resin composition of the present invention can be used in industrial light panels, lighting plates, and other lights used in LCD / LED TVs, notebook computers, mobile phones, and the like.

As described above with reference to a preferred embodiment of the present invention, those skilled in the art or those skilled in the art without departing from the spirit and scope of the present invention described in the claims below It will be appreciated that various modifications and variations can be made in the present invention.

Claims (7)

delete delete Azobisisobutyronitrile, azobis isopentironitrile and at least one of a methyl acrylate compound, an ethyl acrylate compound and a butyl acrylate compound using a monomer comprising at least one acrylate group and a methacrylate group as a solvent 30 to 70% by weight of an acrylic acrylate compound obtained by polymerizing a reaction catalyst selected from the group consisting of azobis methylpropion amidine;
20 to 60% by weight of a reactive monomer comprising at least one vinyl group, acrylate group or methacrylate group;
Urethane acrylate 0.1-15 wt%; And
A photocurable resin composition having PMMA adhesion, comprising 0.5 to 10% by weight of a photopolymerization initiator. The method of claim 3 wherein the reactive monomer is acryloyl morpholine, benzyl acrylate, cyclohexyl acrylate, phenoxy ethyl acrylate, phenoxy diethylene glycol acrylate, phenoxy tetra ethylene glycol acrylate, phenoxy hexa Ethylene glycol acrylate, dicyclo pentadiene acrylate, ortho phenylphenoxy ethyl acrylate, 4-hydroxy butyl acrylate, cyclohexane di methanol mono acrylate, neopentyl acrylate, tripropylene glycol diacrylate, polyethylene Glycol diacrylate, tris (2-hydroxyethyl) isocyanurate diacrylate, dimethylol tricyclodecane diacrylate, ethylene oxide addition type bisphenol A diacrylate, ethylene oxide 3 mole addition type trimethylol propane triacrylate , Ethylene oxide 6 mole addition type trimethylol propane triacrylate, pentaerythritol triacrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexa acrylate and caprolactone modified dipentaerythritol hexa acrylate Resin composition, characterized in that at least one compound selected from the group consisting of. According to claim 3, wherein the urethane acrylate is at least one compound selected from the group consisting of polycarbonate urethane modified acrylate, polyether urethane modified acrylate, polyester urethane modified acrylate and polycaprolactone urethane modified acrylate Resin composition characterized by the above-mentioned. The benzophenone and its derivatives, benzoin, benzoin alkyl ether benzyl dimethyl ketal, 1-hydroxy cyclohexyl phenyl ketone, diethoxyacetophenone, phosphine oxide type, amino acetophenone type, At least one selected from the group consisting of 2-hydroxy-2-methyl-1-phenylpropano-1-non and 2-benzyl-2-dimethylamide-1- (4-morpholinaphenyl) -butanane It is a compound, The resin composition characterized by the above-mentioned. Applying a resin composition according to claim 3 on a polymethyl methacrylate (PMMA) material; And
A method of manufacturing a light guide plate (LGP) comprising the step of photocuring the resin composition to form a film.