KR101330784B1 - Polymer having low molecular weight, preparing method thereof, optical resin composition comprising the same, and optical sheet thereof for display - Google Patents

Abstract

The present invention provides an oligomer represented by the following formula (1), a method for preparing the same, an optical resin composition comprising the same, and an optical sheet prepared therefrom.

Formula 1

The oligomer according to the present invention includes a functional group capable of imparting stability to ultraviolet rays and a functional group acting as an antistatic agent, thereby preventing the polymer resin from turning yellow by ultraviolet rays, and minimizing defects caused by static electricity. In addition, it has an acrylic functional group so that it can be included in the polymer network structure, it is possible to suppress the contamination of the optical sheet prepared from it over time.

Antistatic * Low Polymer * Optical Sheet * Composition * Yellowing Prevention

Description

Polymer having low molecular weight, preparing method according to the present invention, an optical resin composition comprising the same, and an optical sheet comprising the same, and an optical sheet composition for the same.

The present invention relates to a low polymer, a method for preparing the same, an optical resin composition comprising the same, and an optical sheet for a display prepared therefrom, wherein the low molecular weight can minimize the yellowing characteristic of the resin turning yellow when exposed to ultraviolet rays. It relates to a polymer and an optical sheet using the same.

A liquid crystal display (LCD), which is a kind of display, has a light source for irradiating light, a light guide plate or a diffuser plate for uniformly spreading the light emitted from the light source, and the light passing through the light guide plate or the diffuser plate is uniformly It has a back light unit composed of an optical sheet for reaching the front of the liquid crystal display.

The optical sheet used in such a display is exposed to ultraviolet light for a long time, and thus a yellowing phenomenon occurs in which the optical sheet turns yellow. This phenomenon causes the display not to display the correct color by making the entire area of the display appear yellow.

In addition, the optical sheet is made of a polymer resin to induce static electricity, which causes static marks to damage the product, and lower the brightness. In addition, when the optical sheets are stacked in several sheets, the direction is distorted, and when the backlight unit is viewed with the naked eye, dust adheres to cause defects due to foreign matters.

Meanwhile, in the related art, an ultraviolet stabilizer selected from the following Chemical Formulas I to VI was used to prevent yellowing as described above.

In addition, various types of antistatic materials have been included to prevent static electricity.

However, in the polymer resin that makes the optical sheet, these additives act like foreign matter and are not completely contained in the polymer network, so they elute to the surface of the optical sheet and discolor to black over time. Thus, UV stabilizers and antistatic agents There was a limit to the chemical properties as.

Therefore, in the present invention, to solve the problems of the prior art as described above, various additives added as an ultraviolet stabilizer and an antistatic agent in the manufacture of the optical sheet does not play a role, and act as foreign matter This is to solve problems such as yellowing phenomenon.

Accordingly, in the present invention, by preparing to include all of the UV stabilizer, antistatic agent, and the polymer forming reactor in the structure of the low polymer for producing polymer resin used as the optical sheet, it has light resistance to ultraviolet rays, can minimize static electricity, yellowing phenomenon This did not occur and could solve the above problems.

Accordingly, it is an object of the present invention to provide an oligomer used as a material of an optical sheet having excellent antistatic properties and ultraviolet stability.

In addition, another object of the present invention is to provide a method for producing a low polymer having the above characteristics.

Further, another object of the present invention is to provide an optical resin composition containing the oligomer.

Still another object of the present invention is to provide an optical sheet for display manufactured from the optical resin composition.

The present invention includes a functional group that acts as an ultraviolet stabilizer and an antistatic agent in the oligomer chain, thereby preventing the polymer resin from turning yellow by ultraviolet rays, and minimizing defects caused by static electricity. The acrylic sheet, which can be included in the polymer net structure within it, prevents the optical sheet from being contaminated over time.

The oligomer of the present invention for achieving the above object is characterized by that represented by the following formula (1).

, 또는

이며, 상기 A에서 R₁은 서로 같거나 다른 것으로서, 각각 수소, 메틸기, 또는 탄소수 1 내지 8의 알코올기이고, Q^-는 할로겐산 계열, 황산 계열, 인산 계열, 초산 계열, 염화초산 계열, 및 파라톨루엔 설폰산 계열로 이루어진 그룹으로부터 선택된 1 종 이상의 산 성분이며, n은 2∼8의 정수이고,In Formula 1, A is

, or

R ₁ in A is the same as or different from each other, and each is hydrogen, a methyl group, or an alcohol group having 1 to 8 carbon atoms, and Q ⁻ is a halogen acid series, a sulfuric acid series, a phosphoric acid series, an acetic acid series, an acetic acid chloride series, and At least one acid component selected from the group consisting of paratoluene sulfonic acid series, n is an integer from 2 to 8,

또는

이며, 상기 B에서 R₂는 수소원자 또는 메틸기이고, p는 2∼8의 정수이며,B in Chemical Formula 1

or

And, in the B R ₂ is a hydrogen atom or a methyl group, p is an integer from 2 to 8,

이며, 상기 C에서 m은 2∼8의 정수이며, R₃는 수소원자 또는 -(CH₂)cCH₃, -OCH₃, -OCH₂CH₃, -OCH(CH₃)₂, -OC(CH₃)₃ 이며, 여기서 상기 c는 0~6의 정수이다. In Formula 1 C is

And, in the C m is an integer of 2~8, R ₃ is a hydrogen atom or _{- (CH 2) cCH 3,} -OCH 3, -OCH 2 CH 3, -OCH (CH 3) 2, -OC (CH ₃ ) ₃ , where c is an integer of 0 to 6;

In addition, a method for preparing a oligomer for achieving another object of the present invention comprises the steps of: neutralizing the amine compound and acid to synthesize a quaternary ammonium salt; And adding and reacting the quaternary ammonium salt, the compound forming the polymer net structure, and the ultraviolet stabilizer to the polyfunctional isocyanate compound.

In addition, the optical resin composition for achieving another object of the present invention is characterized in that it comprises 100 to 300 parts by weight of the reactive diluent and 0.5 to 5 parts by weight of the photoinitiator with respect to 100 parts by weight of the oligomer represented by the formula (1) do.

Moreover, the optical sheet for achieving the further another objective of this invention is characterized by what was obtained from the said resin composition.

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

The present invention provides an oligomer including both antistatic properties, a functional group forming a polymer net structure, and a structure serving as a UV stabilizer. As used throughout the description and claims, the meaning of "polymer" may be defined as a polymer having a weight average molecular weight of less than 5,000.

First, the antistatic property, the substituent corresponding to A in the oligomer represented by Formula 1 may play a role.

The A substituent is a quaternary ammonium salt obtained by neutralizing a amine compound and an acid component. The amine compounds used at this time include primary, secondary and tertiary amines having 1 to 8 carbon atoms containing at least one hydroxy group (-OH) at the alkyl chain terminal; Secondary and tertiary amines in which a monohydroxy primary amine is substituted with an alkyl chain having 1 to 8 carbon atoms; Secondary and tertiary amines substituted with an alkyl group having 1 to 9 carbon atoms; And amines in which an alkoxy group having 1 to 8 carbon atoms is substituted.

Specific examples of primary, secondary and tertiary amines having 1 to 8 carbon atoms containing at least one hydroxy group (-OH) at the alkyl chain terminal include monoethanol amine and monopropanol amine. (mono-propanol amine), mono-butanol amine, mono-pentanol amine, mono-hexanol amine, monoheptanol amine And mono-octanol amine (mono-octanol amine) is one or more selected from the group consisting of, for example, as shown by the following formula.

In addition, examples of the secondary or tertiary amine in which the C 1-8 alkyl chain is substituted with the monohydroxy primary amine include methyl ethanol amine, ethyl ethanol amine and ethyl di. Ethanol amine (Ethyl diethanol amine), diethanol amine (di-ethanol amine) and triethanol amine (Tri-ethanol amine) can be used any one selected from the group, specific examples thereof are shown in the following formula.

In addition, the secondary and tertiary amines substituted with an alkyl group having 1 to 9 carbon atoms include at least one selected from the group consisting of di-n-butylamine, di-n-propylamine, dimethylamine, and triethylamine, Specifically, it is as follows.

In addition, the amine substituted with a C 1-8 alkoxy (Alkoxy) group containing a hydroxy group in the amine is selected from the group consisting of 2-ethoxy ethylamine, 3-methoxy propylamine, and 3-ethoxy propylamine. It is one or more types, and is specifically, shown by following Chemical formula.

In addition, the acid component used to neutralize the amine compound corresponds to Q ⁻ of A, halogen acid series, sulfuric acid series, phosphoric acid series, acetic acid series, chloride acetate series, paratoluene sulfonic acid series, and At least one selected from the group consisting of derivatives thereof.

The halogen acid sequence is ^{F -, Cl -, Br -} , and I ^- will at least one selected from the group consisting of; Sulfuric acid (sulfuric acid) sequence is _{^{HSO 4 -, SO 4 2 -}} , CH 3 SO4 -, and CH ₃ CH ₂ SO ₄ ^- will at least one selected from the group consisting of; Phosphate (phosphoric acid) family of _{^{H 2 PO 4 -, HPO 3}} 2 - and PO ₄ ^{3 -} will at least one selected from the group consisting of; Acetic acid series is CH ₃ COO ⁻ ; Acid chloride (Chloro acetic acid) based columns _{^{CH 2 ClCOO -, CHCl 2 COO}} - , and CCl ₃ COO ^- will at least one selected from the group consisting of; The para-toluene sulfonic acid family is CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ .

Specific examples of the acid component include chloric acid, sulfuric acid, phosphoric acid, acetic acid, monochloro acetic acid, trichloro acetic acid, Trifluoro acetic acid, fluoric acid, bromic acid, para-toluene sulfonic acid, dimethyl sulfate, diethyl sulfate, and At least one selected from the group consisting of derivatives thereof, but is not limited thereto.

Reaction conditions of the amine-based compound and the acid component may vary depending on the type of amine used, preferably added dropwise under the condition that the maximum reaction temperature does not exceed 50 ℃, stirred for about 1 hour after the addition is completed, the The reaction ratio of the amine compound and the acid component is preferably 1: 0.8 to 0.8: 1 in view of reactivity.

The quaternary ammonium salt represented by A is synthesized by the reaction of the amine compound and the acid component as described above.

In addition, the oligomer according to the present invention represented by the formula (1) uses a B substituent and a UV stabilizer to form a polymer network structure in the future.

B forming the polymer network structure is hydroxyethyl acrylate (hydroxy ethyl acrylate), hydroxyethyl methacrylate (hydroxyethyl methacrylate), hydroxypropyl acrylate ((hydroxypropyl acrylate), hydroxypropyl methacrylate (( hydroxypropyl methacrylate), and at least one acrylic compound selected from the group consisting of ester compounds thereof.

C, which acts as a UV stabilizer, is a piperidine derivative substituted at the opposite end of an alcohol hydroxyl group (-OH), and commercially available products that act as UV stabilizers are generally available. Of these piperidine derivatives, in particular, 2,2,6,6-tetramethyl piperidine derivatives having four methyl groups at the carbon positions of 2,2,6,6 are generally used. It is possible to combine an alkyl group (Alkyl), an alkoxy group (Alkoxy).

On the other hand, the oligomer according to the present invention is a compound A exhibiting the antistatic properties and the compound B to form a polymer network structure, the compound C acting as a UV stabilizer hexamethylene diisocyanate (HMDI) tri represented by the following formula (2) It is prepared by reacting with Trimer.

Since one molecule of the HMDI trimer is a 3-equivalent polyfunctional compound having three isocyanate (N = C = O) groups, the reaction allows each of the compounds A, B, and C to be bound per molecule of HMDI Trimer. . That is, 3 equivalents of the polyfunctional isocyanate represented by Formula 2 and 1 equivalent of the compound represented by A, 1 equivalent of the compound represented by B, and 1 equivalent of the compound represented by C are reacted according to the present invention. To produce an oligomer.

As described above, the oligomer prepared according to the present invention has a weight average molecular weight of 800 to 4,500, preferably 800 to 1,500.

On the other hand, the present invention is also characterized in that it provides an optical resin composition comprising the oligomer prepared as described above.

Such an optical resin composition is prepared by mixing the oligomer with a reactive diluent and a photoinitiator.

The reactive diluent included in the optical resin composition may be selected from the group consisting of butyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and a corresponding acrylic monomer. As one or more, it may be added to lower the viscosity of the oligomer and also act as a reactive diluent added with the following photoinitiators to contribute to the polymer reaction with the oligomer, the content of which is antistatic oligomer 100 It is used by mixing in 100-300 weight part with respect to a weight part.

In addition, a photoinitiator may be added for photocuring the oligomer. The photoinitiator is a photopolymerization initiator is 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) -6- Triazine compounds such as triazine and 2,4-trichloromethyl- (piflonil) -6-triazine; Acetophenone compounds such as 1-hydroxycyclohexyl phenyl ketone and 4- (2-hydroxyethoxy) -phenyl (2-hydroxy) propyl ketone; Benzophenone compounds such as benzophenone and 2,4,6-trimethylaminobenzophenone; 2,2-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5 ' -At least one compound selected from biimidazole-based compounds such as tetrakis (3,4,5-trimethoxyphenyl) -1,2'-biimidazole and the like, from 0.5 to 100 parts by weight of the oligomer. 5 parts by weight is mixed. The photoinitiator can be used alone or in combination.

 In this invention, the display optical sheet manufactured from the above optical resin composition also has the characteristics. The optical sheet may be prepared by applying a thickness of 30 to 250 μm on at least one base film selected from the group consisting of polyester, polycarbonate, polystyrene, and polymethylmethacrylate, and then curing with ultraviolet rays or electron beams. .

Hereinafter, the present invention will be described in more detail with reference to the following Examples, but the present invention is not limited thereto.

Synthetic example  1: Compound A (quaternary ammonium salt exhibiting antistatic properties) Manufacturing example

Into a 2L resin kettle equipped with a strong stirrer, thermometer, dropping funnel, condenser and cooling jacket, 62 g of ethanol amine (Aldrich, USA) was added dropwise slowly to 49 g of 98% sulfuric acid (Aldrich, USA). The reaction temperature was completely added dropwise while being careful not to exceed 50 ° C, followed by stirring at room temperature for 1 hour, thereby exhibiting antistatic properties and synthesizing A-1 having a weight average molecular weight 111.

Synthetic example  2: A compound (quaternary ammonium salt exhibiting antistatic properties) Manufacturing example

Into a 2L resin kettle equipped with a strong stirrer, thermometer, dropping funnel, condenser and cooling jacket, 62 g of ethanol amine (Aldrich, USA) was added dropwise slowly to 114 g of trifluoroacetic acid (Aldrich, USA). The reaction temperature was added dropwise while being careful not to exceed 50 ° C, followed by stirring at room temperature for 1 hour to synthesize antistatic properties, indicating A-2 having a weight average molecular weight of 176.

Example  One : Oligomer Manufacturing example

Hydroxyethyl methacrylate (Aldrich, USA) that forms a polymer network with 504 g equivalent to 3 equivalents of HMDI in a 4L resin kettle equipped with a strong stirrer, thermometer, dropping funnel, condenser and cooling jacket 1 130 g of the equivalent was slowly added dropwise. The reaction temperature was added dropwise while being careful not to exceed 50 ° C, and stirred at room temperature for 1 hour. To this, 111 g (1 equivalent) of A-1 exhibiting the antistatic properties of Synthesis Example 1 was added dropwise while being careful not to exceed the reaction temperature of 50 ° C., and stirred at room temperature for 1 hour 40 minutes.

2- (2,2,6,6-tetramethyl-piperidin-4-yl) -ethanol (2- (2,2,6,6-tetramethyl-piperidin-4-yl, which acts as a UV stabilizer here) ) -ethanol, Aldrich Co., Ltd.) 185 g (1 equivalent) was added dropwise while being careful not to let the reaction temperature exceed 50 ° C., followed by stirring at room temperature for 2 hours to obtain a polymer having a weight average molecular weight of 930.

The oligomer of the present invention is NCO%: 13.22 after the first reaction (hydroxyethyl methacrylate reaction), NCO% after the second reaction (antistatic compound): 5.62, NCO after the third reaction (ultraviolet stabilizer compound) As%: 0, the polyfunctional isocyanate content participating in the reaction was calculated to confirm that the reaction proceeded completely.

Example  2 : Oligomer Manufacturing example

As a compound exhibiting antistatic properties, a low polymer according to the present invention having a weight average molecular weight of 995 was obtained in the same manner as in Example 1, except that 176 g (1 equivalent) of A-2 of Synthesis Example 2 was added.

The oligomer of the present invention is NCO% after the first reaction (hydroxyethyl methacrylate reaction): 13.22, NCO% after the second reaction (antistatic property compound): 5.20, NCO after the third reaction (ultraviolet stabilizer compound) %: 0 As a result, the content of the polyfunctional isocyanate participating in the reaction was calculated to confirm that the reaction proceeded completely.

Example  3: optical resin composition Manufacturing example

To 50 g of the oligomer of Example 1, 50 g of butyl acrylate, which is a reactive diluent, and 3 g of a photoinitiator benzophenone were added and mixed to make the optical resin composition uniform.

Example  4: optical resin composition Manufacturing example

An optical resin composition was prepared in the same manner as in Example 3, except that 50 g of the oligomer of Example 2 was used.

The antistatic properties and ultraviolet light resistance of the mixtures of Examples 3 and 4 prepared above, and a sample containing 100 g of butyl acrylate and 3 g of benzophenone uniformly without including the oligomer according to the present invention as a reference sample The properties were measured as follows, and the results are shown in Table 1 below.

< Experimental Example >

Based on the PET film, the composition obtained through the above examples and the reference sample was uniformly coated at 50 to 250 μm, and cured with a UV lamp having a wavelength of 365 nm to prepare an optical sheet. In addition, the physical properties of each sheet prepared above were evaluated as follows.

-UV exposure test is based on 500 hours at 60 ° C UVA lamp, 0.77W / ㎠ with QUV equipment.

-The smaller the value, the better the antistatic property. The UV light resistance means that the b * value is changed to a deeper yellow.

Right after curing after coating After 500 hours of UV exposure
standard
sample Antistatic property
(Surface resistance) 7 × 10 ¹⁴ Ω / ㎠ 5 × 10 ¹⁴ Ω / ㎠ UV light resistance L ^* : 81.50
a ^* : 2.70
b ^* : -1.60 L ^* : 82.1
a ^* : 2.71
b ^* : -0.61
Example 3 Antistatic property
(Surface resistance) 4 × 10 ¹¹ Ω / ㎠ 1 × 10 ¹² Ω / ㎠ UV light resistance L ^* : 81.42
a ^* : 2.59
b ^* : -1.62 L ^* : 81.51
a ^* : 2.67
b ^* : -1.49
Example 4 Antistatic property
(Surface resistance) 2 × 10 ⁹ Ω / ㎠ 9 × 10 ⁹ Ω / ㎠ UV light resistance L ^* : 82.09
a ^* : 2.71
b ^* : -1.61 L ^* : 82.71
a ^* : 2.73
b ^* : -1.43

As shown in the results of Table 1, the optical sheet prepared from the optical resin composition comprising the oligomer according to the present invention exhibits excellent antistatic properties with a surface resistance of 10 ¹⁴ Ω / cm 2 or less, and yellow even when exposed to ultraviolet rays for a long time. It is possible to improve the reliability of the optical sheet used in the display by exhibiting the ultraviolet light resistance characteristics that do not change.

Although the present invention has been described in accordance with embodiments of the present invention, modifications and variations may be made by those skilled in the art without departing from the technical spirit of the present invention.

Claims (11)

The oligomer represented by the following formula (1). Formula 1

In Formula 1, A is

, or

R ₁ in A is the same as or different from each other, and each is hydrogen, a methyl group, or an alcohol group having 1 to 8 carbon atoms, and Q ⁻ is a halogen acid series, a sulfuric acid series, a phosphoric acid series, an acetic acid series, an acetic acid chloride series, and At least one acid component selected from the group consisting of paratoluene sulfonic acid series, n is an integer from 2 to 8, B in Chemical Formula 1

or

And, in the B R ₂ is a hydrogen atom or a methyl group, p is an integer from 2 to 8, In Formula 1, the terminal C is

And, in the C m is an integer of 2~8, R ₃ is a hydrogen atom or _{- (CH 2) cCH 3,} -OCH 3, -OCH 2 CH 3, -OCH (CH 3) 2, -OC (CH ₃ ) ₃ , where c is an integer of 0 to 6;  The oligomer according to claim 1, wherein the oligomer has a weight average molecular weight of 800 to 4500. Neutralizing the amine compound and an acid to synthesize a quaternary ammonium salt; And The quaternary ammonium salt and acryl-based compound in the polyfunctional isocyanate compound And adding a UV stabilizer and reacting the oligomer represented by the following Chemical Formula 1. Formula 1

In Formula 1, A is

, or

R ₁ in A is the same as or different from each other, and each is hydrogen, a methyl group, or an alcohol group having 1 to 8 carbon atoms, and Q ⁻ is a halogen acid series, a sulfuric acid series, a phosphoric acid series, an acetic acid series, an acetic acid chloride series, and At least one acid component selected from the group consisting of paratoluene sulfonic acid series, n is an integer from 2 to 8, B in Chemical Formula 1

or

And, in the B R ₂ is a hydrogen atom or a methyl group, p is an integer from 2 to 8, In Formula 1, the terminal C is

And, in the C m is an integer of 2~8, R ₃ is a hydrogen atom or _{- (CH 2) cCH 3,} -OCH 3, -OCH 2 CH 3, -OCH (CH 3) 2, -OC (CH ₃ ) ₃ , where c is an integer of 0 to 6; The method of claim 3, wherein the amine-based compound comprises at least one hydroxy group (-OH) having at least one hydroxy group (-OH) at 1 to 8 carbon atoms, secondary and tertiary amines; Secondary and tertiary amines in which a monohydroxy primary amine is substituted with an alkyl chain having 1 to 8 carbon atoms; Secondary and tertiary amines substituted with an alkyl group having 1 to 9 carbon atoms; And at least one member selected from an amine substituted with an alkoxy group having 1 to 8 carbon atoms. The method of claim 3, wherein the acid component is at least one selected from the group consisting of halogenic acid series, sulfuric acid series, phosphoric acid series, acetic acid series, chloride acetate series, and paratoluene sulfonic acid series. The method of claim 5, wherein the acid component is chloric acid (sulfuric acid), sulfuric acid (sulfuric acid), phosphoric acid (phosphoric acid), acetic acid (Acetic acid), monochloro acetic acid (monochloro acetic acid), trichloro acetic acid (trichloro acetic acid) , Trifluoro acetic acid, fluoric acid, bromic acid, para-toluene sulfonic acid, dimethyl sulfate, diethyl sulfate A process for producing an oligomer, characterized in that at least one member selected from the group consisting of: The method of claim 3, wherein the acrylic compound is hydroxyethyl acrylate (hydroxy ethyl acrylate), hydroxyethyl methacrylate (hydroxyethyl methacrylate), hydroxypropyl acrylate ((hydroxypropyl acrylate), hydroxypropyl methacrylate ( (hydroxypropyl methacrylate), hydroxy alkyl (meth) acrylate (hydroxy alkyl (meth) acrylate), and a method for producing a low polymer, characterized in that at least one selected from the group consisting of ester compounds thereof. Butyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and the like, relative to 100 parts by weight of the oligomer according to claim 1. Optical resin composition containing 1 to 100 to 300 parts by weight and 0.5 to 5 parts by weight of photoinitiator selected from the group consisting of acrylic monomers. delete The optical resin composition according to claim 8, wherein the photoinitiator is at least one compound selected from triazine compounds, acetophenone compounds, benzophenone compounds, and biimidazole compounds. The optical sheet for display obtained from the optical resin composition of Claim 8.