KR102549521B1 - Resin for photosensitive composition - Google Patents

Abstract

The present invention relates to a resin for a photosensitive composition, comprising: a first monomer of structural formula 1; A second monomer of Structural Formula 2; and a backbone in which the third monomer of Structural Formula 3 is polymerized and a fourth monomer which is an epoxy monomer bonded to the backbone and having an ethylenically unsaturated group for acid value control.

Description

Resin for photosensitive composition

The present invention relates to resins for photosensitive compositions.

Recently, a liquid crystal display device and an OLED display device are widely used, and a new type of display device is also being developed.

In particular, recent display devices are endowed with functions that can be folded or rolled around mobile devices.

A resin layer is used in the display device to maintain a gap or the like. The resin layer (photosensitive layer) is formed through a process of coating and curing a photosensitive composition composed of a monomer, resin, and photoinitiator, and a patterning process may be added in some cases. The resin layer may be present in the form of a coating film in a display device.

The resin layer should have high elongation and elasticity, and should not be damaged even when repeated force is applied. In addition, the optical characteristics should not be degraded by the light source of the display device.

The physical properties of the resin layer are largely determined by the resin, and it is necessary to develop a resin to satisfy these physical properties.

Korean Publication No. 2004-0030848 (published on April 9, 2004)

Accordingly, an object of the present invention is to provide a resin for a photosensitive composition.

An object of the present invention is to provide a resin for a photosensitive composition comprising: a first monomer of structural formula 1; A second monomer of Structural Formula 2; And a backbone in which the third monomer of structural formula 3 is polymerized.

<Structural Formula 1>

<Structural Formula 2>

<Structural Formula 3>

Here, X represents a hydrogen atom or a methyl group, R1 represents an alkyl group having 1 to 3 carbon atoms, R2 represents an alkyl group having 3 to 20 carbon atoms, and the carbon number of R2 is greater than that of R1. It is achieved by including a fourth monomer which is an epoxy monomer bonded to the backbone and having an ethylenically unsaturated group for acid value control.

The alkyl group may be linear, branched or cyclic, and some or all of the hydrogen atoms may be substituted with substituents.

The first monomer and the second monomer may independently be any one of (meth)acrylic acid esters and (meth)acrylic acid alkyl esters.

The fourth monomer may include at least one selected from Structural Formulas 4 and 5 below.

<Structural Formula 4>

<Structural Formula 5>

Here, R3 and R4 are, independently, hydrogen or a methyl group.

In the backbone, the first monomer may be 5 to 60% by weight, the second monomer may be 20 to 90% by weight, and the third monomer may be 5 to 30% by weight.

In the backbone, the first monomer may be 35 to 45% by weight, the second monomer may be 30 to 50% by weight, and the third monomer may be 10 to 20% by weight.

The fourth monomer may be 5 to 25 parts by weight based on 100 parts by weight of the backbone.

According to the present invention, a resin for a photosensitive composition is provided.

The present invention will be described in more detail with reference to the following drawings.

Since the accompanying drawings are only examples shown to explain the technical spirit of the present invention in more detail, the spirit of the present invention is not limited to the accompanying drawings. In addition, in the accompanying drawings, sizes and intervals may be exaggerated unlike actual ones in order to explain the relationship between each component.

The 'resin' in the present invention may also be called a 'copolymer' or 'oligomer'. The resin of the present invention can be used as a component of a photosensitive composition. The use of the photosensitive composition is not limited to display devices. The photosensitive composition forms a resin layer through processes such as application and curing.

The resin of the present invention is composed of a backbone comprising three monomers and a fourth monomer connected to the backbone.

The weight average molecular weight (Mw) of the resin may be 5,000 to 50,000 or 15,000 to 22,000. If the weight average molecular weight (Mw) exceeds 50,000, printability and solubility in solvents are considerably deteriorated due to high viscosity, so that excellent photosensitive coatings cannot be made. In addition, when the weight average molecular weight (Mw) is 5,000 or less, it is easy to form a photosensitive coating film, but formability and adhesion may be deteriorated.

The first monomer, the second monomer and the third monomer forming the backbone will be described.

The first monomer is represented by the following Structural Formula 1 and the second monomer is represented by the following Structural Formula 2.

<Structural Formula 1>

<Structural Formula 2>

In the structural formula, X may be a hydrogen atom or a methyl group. The rate of UV curing can be controlled according to the hydrogen atom or methyl group. When X is a methyl group, strength and transmittance may be good, but light curing speed or curing conversion rate may be deteriorated.

R1 represents an alkyl group having 1 to 3 carbon atoms, and R2 represents an alkyl group having 3 to 20 carbon atoms.

Here, the carbon number of R2 is greater than that of R1, and may be 2 or more, 5 or more, 8 or more, or 10 or more.

The alkyl group may be linear, branched or cyclic, and specific examples include methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t -It may be a butyl group, a cyclobutyl group or an n-pentyl group. Some or all of the hydrogen atoms of the alkyl group may be substituted with a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an amino group.

Specific examples of the first monomer and the second monomer are as follows. Examples of the (meth)acrylic acid ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, and hexyl (meth)acrylate. Among the (meth)acrylic acid alkyl esters, there are (meth)acrylic acid esters having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, hydroxy (meth)acrylate, and hydroxybutyl (meth)acrylate. there is. (meth)acrylic acid esters having a hydroxyl group such as lactone-modified capronlactone-modified 2-hydroxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, and ethoxydiethylene glycol (meth)acrylate Alkoxyalkylene glycol mono, such as isooctyloxydiethylene glycol (meth)acrylate, phenoxytriethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate (meth)acrylate etc. are mentioned.

The resin includes a first monomer and a second monomer to improve adhesion and gloss after curing.

The backbone of the resin includes a third monomer for ring-opening polymerization, improvement of the dispersibility of the filler, and improvement of adhesion to the substrate.

The third monomer may be represented by Structural Formula 3 below.

<Structural Formula 3>

The resin has the same acidic group as the third monomer.

As a compound used by substitution with a part of acrylic acid, methacrylic acid, acrylic acid, etc. are mentioned as a compound which contains an unsaturated group and has at least 1 acid value at the same time.

The acidic group is not particularly limited, and an appropriate one can be selected and used from known ones. Among them, those that are excellent in developability and water resistance of the cured film, are easy to disperse in the filler, and can improve adhesion to the base material are advantageous. should be used

The resin includes a fourth monomer bound to the backbone. The fourth monomer is an epoxy monomer having an ethylenically unsaturated group and can facilitate UV curing of the photosensitive composition.

The fourth monomer may be represented by Structural Formula 4 or Structural Formula 5.

<Structural Formula 4>

<Structural Formula 5>

R3 and R4 in Structural Formulas 4 and 5 independently represent hydrogen or a methyl group. When R3 and R4 are hydrogen, the curing speed is fast during UV curing, but the strength of the solidified film is weak. When R3 and R4 are methyl groups, the curing speed is somewhat slow, but the strength of the solidified film is high and chemical resistance is improved. effect can be obtained. Structural formula 4 is an epoxy monomer having an alicyclic ethylenically unsaturated group, and structural formula 5 is an epoxy monomer having a branched ethylenically unsaturated group.

Although there is no restriction|limiting in particular as an ethylenically unsaturated group, A (meth)acryloyl group is preferable. In addition, ethylenically unsaturated monomers may be used alone or in combination.

5 to 60% by weight of the first monomer, 20 to 90% by weight of the second monomer and 5 to 30% by weight of the third monomer in the backbone of the resin, or 35 to 45% by weight of the first monomer and 30% by weight of the second monomer to 50% by weight and the third monomer may be 10 to 20% by weight.

The fourth monomer may be 5 to 25 parts by weight based on 100 parts by weight of the backbone.

The first monomer serves to improve gloss, and when excessively included, there is a problem in that it becomes hard and cracking occurs. On the other hand, when it is included too little, the effect of improving gloss is insignificant.

The second monomer affects flexibility. When an excessive amount of the second monomer is included, a problem of becoming hard occurs.

The third monomer is necessary for reaction with the fourth monomer, and when it is too small, it becomes difficult to remove the uncured film, and when it is excessive, water resistance and electrical properties tend to deteriorate.

The fourth monomer is necessary for photocuring, and when it is too small, a problem of low UV curability occurs, and when it is excessive, a problem occurs in storage safety.

Copolymerization for preparing the resin may be carried out in a two-step process, which is a copolymerization reaction process of the first to third monomers and a process of introducing a fourth monomer containing an ethylenically unsaturated group. First, in the copolymerization reaction, a copolymerization reaction of various monomers is carried out, but there is no particular restriction on the copolymerization reaction, and it can be appropriately selected from known ones. For example, radical polymerization, cationic polymerization, coordination polymerization, etc. can be selected for the active species of polymerization. Among these, since synthesis is easy and low cost, radical polymerization is preferable. Also, there is no particular restriction on the polymerization method, and it can be selected from well-known methods. For example, a bulk polymerization method, a suspension polymerization method, an emulsion neutralization method, a solution polymerization method, or the like can be appropriately selected. Among these, a solution polymerization method is more preferable.

The resin according to the present invention may be supplied in a solution state containing the solvent used in the polymerization process and/or a separate solvent. The content of the resin in the solution state may be 20 to 80% by weight or 40 to 60% by weight.

The boiling point of the solvent may be 80 °C to 300 °C or 120 °C to 200 °C. As the solvent, known solvents may be used, and may be selected and used according to the conditions of copolymerization. When a solvent within the above boiling point range is used, the evaporation rate may be lowered during the copolymerization reaction, and the heat curing temperature and production process of the photosensitive resin composition may be suitable.

Specific examples of the solvent include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol isopropyl ether, and ethylene glycol monobutyl Ether, Ethylene Glycol Dibutyl Ether, Ethylene Glycol Monohexyl Ether, Ethylene Glycol Monobenzyl Ether, Ethylene Glycol Monophenyl Ether, Ethyl Glycol Monoacetate, Ethylene Glycol Di Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene Glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethyl Leglycol Dibutyl Ether, Diethylene Glycol Monohexyl Ether, Diethylene Glycol Monobenzyl Ether, Diethylene Glycol Monophenyl Ether, Diethylene Glycol Acetate, Diethylene Glycol Mono Ethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether , Propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono Butyl ether, tripropylene glycol monomethyl ether, trimethylene glycol, hexylene glycol, octylene glycol, methoxymethoxyethanol, 1-butoxyethoxypropanol, isobutyl acid ester, 2-ethylhexyl acetate, acyclohexyl acetate, methylcyclohexyl acetate, isoamyl acetate, n-butyl propionate, isobutyl lactate, n-butyl lactate, isobutyl lactate, n-butyl lactate, n-butyl lactate, lactic acid n-Amyl, isoamyl lactate, isoamyl isovalate, ethyl acebutyrate, butyl stearate, dibutyl oxylate, diethyl malonate, ethyl benzoate, methyl benzoate, propyl benzoate, methyl salicylate, methylphenyl ether, ethylbenzyl Ether, ethylphenyl ether, dichloroethyl ether, diisoamyl ether, n-hexyl ether, 1,4-dioxane, diethyl acetal, cineol, methyl ethyl ketone, methyl butyl ketone, methyl iso Butyl ketone, diethyl ketone, ethyl n-butyl ketone, acetonylacetone, phorone, isophorone, acetophenone, glycerin, butanol, 2-butanol, 1,3-butanediol, 2,3-butanedi alcohol, isoamyl alcohol, 1,5-pentanediol, 2-methylcyclohexanol, 2-ethylhexanol, 3,5,5-trimethylhexanol, 1-octanol, 2-octanol, nonanol , n-decanol, triglyalcohol, benzyl alcohol, alpha-termineol, tetrahydrofurfuryl alcohol, abietinol, trichloride, trichloroacetic acid, lactic acid, valeric acid, isovaleric acid, caprosine , 2-ethyl nucleic acid, caprylic acid, butyric anhydride, decane, dipente, p-methane, dodecane, 1,1,2-trichloroethane, 1,1,1,1,2-tetrachloro Ethane, 1,1,2,2-tetrachloroethane, hexanechloroethane, toluene, xylene, o-dichlorobenzene, p-dichlorobenzene, 1,2,4-trichlorobenzene, o-dibromobenzene , benzonitrile, nitrobenzene, alpha-tolunitri (phenylacetonitrile), N-methylformamide, N-methylacetamide, 2-pyrrolidone, and the like.

A solvent can be used individually by 1 type or in mixture of 2 or more types. The boiling point of the solvent is preferably 150°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher, from the viewpoint of printability. Examples of such solvents include diethylene glycol monomethyl ether, diethylene glycol, monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, and diethyl glycol. Monobutyl ether acetate, diethyl glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol monohexyl ether, triethyl glycol Monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monoethyl ether, diethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monobenzyl ether and the like are particularly preferred.

The present invention will be described in detail through Examples and Comparative Examples below.

Example 1

In a 2-liter separable flask equipped with a stirrer, thermometer, heating mantle, reflux condenser, dropping funnel and nitrogen inlet pipe, 629 g of dipropylene glycol monomethyl ether (MFDG manufactured by Hannong Chemical) was introduced, and the temperature was raised to 80 ° C. Methacrylic acid 94.35 g, lauryl methacrylate (Green Chemical Comerate A-1290M) 754.77 g, methyl methacrylate (LG MMA) 94.35 g and 2,2''-azobis (2,4-di 29.17 g of methylpentanenitrile) (manufactured by Wako Pure Chemical Industry, V-65) was added dropwise together over 1 hour. After dropping, the mixture was aged for 3 hours, and a major polymer having a carboxyl group was synthesized. Next, 94.43 g of 3,4-epoxycyclohexylmethyl methacrylate (TTA15 manufactured by Jiangsu Tetra), 6.02 g of benzyltriethylammonium chloride, and 1.05 g of 4-methoxyphenol were added to the main polymer solution, and the mixture was heated at 100 ° C for 5 time reacted. The reaction was conducted under a mixed atmosphere of air/nitrogen. Thus, a resin solution having an acid value of 26 mgKOH/g and a weight average molecular weight of 14,000 was obtained.

Example 2

In a 2-liter separable flask equipped with a stirrer, thermometer, heating mantle, reflux condenser, dropping funnel and nitrogen inlet pipe, 629 g of dipropylene glycol monomethyl ether (MFDG manufactured by Hannong Chemical) was introduced, and the temperature was raised to 80 ° C. 141.52 g of acrylic acid, 377.38 g of lauryl methacrylate (Commerate A-1290M manufactured by Green Chemical), 424.56 g of methyl methacrylate (manufactured by LG MMA) and 2,2''-azobis (2,4-dimethylpentane) Nitrile) (manufactured by Wako Pure Chemical Industry, V-65) 23.55 g was added dropwise together over 1 hour. After dropping, the mixture was aged for 3 hours, and a major polymer having a carboxyl group was synthesized. Next, 155.53 g of 3,4-epoxycyclohexylmethyl methacrylate (TTA15 manufactured by Jiangsu Tetra), 5.23 g of benzyltriethylammonium chloride, and 0.85 g of 4-methoxyphenol were added to the main polymer solution, and the mixture was heated at 100 ° C for 5 time reacted. The reaction was conducted in a mixed atmosphere of air/nitrogen. As a result, a resin solution having an acid value of 47 mgKOH/g and a weight average molecular weight of 19,000 was obtained.

Example 3

In a 2-liter separable flask equipped with a stirrer, thermometer, heating mantle, reflux condenser, dropping funnel and nitrogen inlet pipe, 629 g of dipropylene glycol monomethyl ether (MFDG manufactured by Hannong Chemical) was introduced, and the temperature was raised to 80 ° C. Acrylic acid 188.69g, lauryl methacrylate (Green Chemical Comerate A-1290M) 94.35g, methyl methacrylate (LG MMA) 94.35g, butyl methacrylate (LGMMA BMA) 566.08g and 2,2' 23.55 g of '-azobis(2,4-dimethylpentanenitrile) (manufactured by Wako Pure Chemical Industry, V-65) was added dropwise over 1 hour. After dropping, the mixture was aged for 3 hours, and a major polymer having a carboxyl group was synthesized. Next, 155.53 g of 3,4-epoxycyclohexylmethyl methacrylate (TTA15 manufactured by Jiangsu Tetra), 5.23 g of benzyltriethylammonium chloride, and 0.85 g of 4-methoxyphenol were added to the main polymer solution, and the mixture was heated at 100 ° C for 5 time reacted. The reaction was conducted in a mixed atmosphere of air/nitrogen. As a result, a resin solution having an acid value of 61 mgKOH/g and a weight average molecular weight of 19,000 was obtained.

Comparative Example 1

In a 2-liter separable flask equipped with a stirrer, thermometer, heating mantle, reflux condenser, dropping funnel and nitrogen inlet pipe, 629 g of dipropylene glycol monomethyl ether (MFDG manufactured by Hannong Chemical) was introduced, and the temperature was raised to 80 ° C. 149.24 g of methacrylic acid, 99.49 g of ethyl methacrylate, and 12.47 g of benzoyl peroxide were added dropwise over 1 hour together. After dropping, the mixture was aged for 3 hours, and a major polymer having a carboxyl group was synthesized. Next, 167.14 g of 3,4-epoxycyclohexylmethyl methacrylate (TTA15 manufactured by Jiangsu Tetra), 6.21 g of benzyltriethylammonium chloride, and 0.51 g of 4-methoxyphenol were added to the main polymer solution, and the mixture was heated at 100° C. for 5 minutes. time reacted. The reaction was conducted in a mixed atmosphere of air/nitrogen. As a result, a resin solution having an acid value of 55 mgKOH/g and a weight average molecular weight of 24,000 was obtained.

Comparative Example 2

In a 2-liter separable flask equipped with a stirrer, thermometer, heating mantle, reflux condenser, dropping funnel and nitrogen inlet pipe, 629 g of dipropylene glycol monomethyl ether (MFDG manufactured by Hannong Chemical) was introduced, and the temperature was raised to 80 ° C. 149.24 g of methacrylic acid, 99.49 g of butyl methacrylate (BMA manufactured by LGMA), and 12.47 g of benzoyl peroxide were added dropwise together over 1 hour. After dropping, the mixture was aged for 3 hours, and a major polymer having a carboxyl group was synthesized. Next, 167.14 g of 3,4-epoxycyclohexylmethyl methacrylate (TTA15 manufactured by Jiangsu Tetra), 6.21 g of benzyltriethylammonium chloride, and 0.51 g of 4-methoxyphenol were added to the main polymer solution, and the mixture was heated at 100° C. for 5 minutes. time reacted. The reaction was conducted in a mixed atmosphere of air/nitrogen. As a result, a resin solution having an acid value of 54 mgKOH/g and a weight average molecular weight of 20,000 was obtained.

Comparative Example 3

In a 2-liter separable flask equipped with a stirrer, thermometer, heating mantle, reflux condenser, dropping funnel and nitrogen inlet pipe, 629 g of dipropylene glycol monomethyl ether (MFDG manufactured by Hannong Chemical) was introduced, and the temperature was raised to 80 ° C. 116.67 g of methacrylic acid, 465.53 g of ethyl methacrylate, and 45.05 g of benzoyl peroxide were added dropwise over 1 hour together. After dropping, the mixture was aged for 3 hours, and a major polymer having a carboxyl group was synthesized. Next, 62.24 g of 3,4-epoxycyclohexylmethyl methacrylate (TTA15 manufactured by Jiangsu Tetra), 3.95 g of benzyltriethylammonium chloride, and 0.7 g of 4-methoxyphenol were added to the main polymer solution, and the mixture was heated at 100° C. for 5 minutes. time reacted. The reaction was conducted in a mixed atmosphere of air/nitrogen. Thus, a resin solution having an acid value of 58 mgKOH/g and a weight average molecular weight of 13,000 was obtained.

Comparative Example 4

In a 2-liter separable flask equipped with a stirrer, thermometer, heating mantle, reflux condenser, dropping funnel and nitrogen inlet pipe, 629 g of dipropylene glycol monomethyl ether (MFDG manufactured by Hannong Chemical) was introduced, and the temperature was raised to 80 ° C. 116.67 g of methacrylic acid, 465.53 g of ethyl methacrylate, and 45.05 g of benzoyl peroxide were added dropwise over 1 hour together. After dropping, the mixture was aged for 3 hours, and a major polymer having a carboxyl group was synthesized. Next, 62.24 g of 3,4-epoxycyclohexylmethyl methacrylate (TTA15 manufactured by Jiangsu Tetra), 3.95 g of benzyltriethylammonium chloride, and 0.7 g of 4-methoxyphenol were added to the main polymer solution, and the mixture was heated at 100° C. for 5 minutes. time reacted. The reaction was conducted in a mixed atmosphere of air/nitrogen. Thus, a resin solution having an acid value of 51 mgKOH/g and a weight average molecular weight of 19,000 was obtained.

Comparative Example 5

In a 2-liter separable flask equipped with a stirrer, thermometer, heating mantle, reflux condenser, dropping funnel and nitrogen inlet pipe, 629 g of dipropylene glycol monomethyl ether (MFDG manufactured by Hannong Chemical) was introduced, and the temperature was raised to 80 ° C. 116.67 g of methacrylic acid, 465.53 g of butyl methacrylate (BMA manufactured by LGMA), and 45.05 g of benzoyl peroxide were added dropwise together over 1 hour. After dropping, the mixture was aged for 3 hours, and a major polymer having a carboxyl group was synthesized. Next, 62.24 g of 3,4-epoxycyclohexylmethyl methacrylate (TTA15 manufactured by Jiangsu Tetra), 3.95 g of benzyltriethylammonium chloride, and 0.7 g of 4-methoxyphenol were added to the main polymer solution, and the mixture was heated at 100° C. for 5 minutes. time reacted. The reaction was conducted in a mixed atmosphere of air/nitrogen. As a result, a resin solution having an acid value of 57 mgKOH/g and a weight average molecular weight of 13,000 was obtained.

Comparative Example 6

In a 2-liter separable flask equipped with a stirrer, thermometer, heating mantle, reflux condenser, dropping funnel and nitrogen inlet pipe, 629 g of dipropylene glycol monomethyl ether (MFDG manufactured by Hannong Chemical) was introduced, and the temperature was raised to 80 ° C. 179.74 g of acrylic acid, 717.24 g of butyl methacrylate (BMA manufactured by LGMA), and 66.78 g of benzoyl peroxide were added dropwise over 1 hour together. After dropping, the mixture was aged for 3 hours, and a major polymer having a carboxyl group was synthesized. Next, 95.06 g of 3,4-epoxycyclohexylmethyl methacrylate (TTA15 manufactured by Jiangsu Tetra), 6.01 g of benzyltriethylammonium chloride, and 1.09 g of 4-methoxyphenol were added to the main polymer solution, and the mixture was heated at 100 ° C for 5 time reacted. The reaction was conducted in a mixed atmosphere of air/nitrogen. Thus, a resin solution having an acid value of 79 mgKOH/g and a weight average molecular weight of 17,000 was obtained.

The types and contents of the monomers in the above Examples and Comparative Examples are summarized in Table 1 below.

The contents of the first monomer, the second monomer, and the third monomer are weight percent in the backbone, and the fourth monomer is a weight part (part) when the backbone is placed in 100 parts by weight (part).

<Table 1>

Table 2 shows the molecular weight of the resins obtained in Examples and Comparative Examples.

<Table 2>

Molecular weight was measured by GPC, and the measurement conditions were as follows.

(1) Analysis instrument: SHIMADZU RID-20A

(2) Pump: LC 20AD

(3) Detector: RID 20A

(4) Solvent: Tetrahydrofuran 99.9%

(5) Column: KF804L (2EA). KF800D(1EA) serial connection

(6) Temperature: 35℃

(7) Flow rate: 0.7 mL/min

(8) Injection amount and sample concentration: 10uL, 10mg/mL

<Preparation of samples for evaluation>

100 parts of the photosensitive resin material prepared in Examples and Comparative Examples, 8 parts of the photocuring initiator, and dipropylene glycol monomethyl ether were adjusted to a weight ratio of 10 to 20% of the photosensitive resin and stirred and mixed, and then the surface of the polyethylene terephthalate film uniformly applied using a bar coater, dried at 95 ° C. for 5 minutes using a dryer, and then cured at 365 or 436 nm light to prepare a solidified sample.

1. Sensitivity measurement

Sensitivity was measured by using a direct exposure device DI exposure machine (dominant wavelength 405 nm) at an exposure amount of 21 steps of the stopper tablet to be 8, and the sensitivity is shown in Table 3.

2. Development

Developability was evaluated by removing PR from a certain area to implement a pattern by dividing necessary and unnecessary parts for development with 1% aqueous sodium carbonate solution (developer). If it develops, it is O, and if it does not develop, it is X.

3. Heat resistance

Heat resistance was determined by observing color change after maintaining at 288° C. for 10 seconds.

4. Gloss measurement

The specular gloss at an angle of 60° of the solidified resin layer (photosensitive layer) of each Comparative Example and Example was immediately determined by the JIS Z 8741 measurement method.

The measured value of gloss was used as a factor to compare the strength of the resin layer (photosensitive layer). One.

<Table 3>

Referring to Table 3, Comparative Examples 2, 5, and 6 in which the first monomer was not used had a problem of insufficient gloss. Comparative Examples 1, 3, and 4 in which the second monomer was not used also did not have sufficient gloss, and in particular, Comparative Examples 3 and 4 had poor developability.

On the other hand, Examples 1, 2, and 3 using all of the first to fourth monomers were excellent in all physical properties such as developability and gloss.

The above-described embodiments are examples for explaining the present invention, but the present invention is not limited thereto. Those skilled in the art to which the present invention pertains will be able to practice the present invention with various modifications therefrom, so the technical protection scope of the present invention should be defined by the appended claims.

Claims (7)

In the resin for the photosensitive composition,
A first monomer of Structural Formula 1;
A second monomer of Structural Formula 2; and
A backbone in which the third monomer of structural formula 3 is polymerized; and
<Structural Formula 1>

<Structural Formula 2>

<Structural Formula 3>

Here, X represents a hydrogen atom or a methyl group, R1 represents an alkyl group having 1 to 3 carbon atoms, R2 represents an alkyl group having 3 to 20 carbon atoms, and the carbon number of R2 is greater than that of R1.
A fourth monomer, which is an epoxy monomer bonded to the backbone and having an ethylenically unsaturated group for acid value control,
Resin, wherein the fourth monomer is bonded to the backbone by reacting with the epoxy group of the fourth monomer and the carboxyl group of the backbone. According to claim 1,
The alkyl group is linear, branched or cyclic, and some or all of the hydrogen atoms are substituted with substituents. According to any one of claims 1 and 2,
The first monomer and the second monomer are independently any one of (meth) acrylic acid esters and (meth) acrylic acid alkyl esters. According to claim 3,
The fourth monomer,
A resin comprising at least one selected from structural formulas 4 and 5 below.
<Structural Formula 4>

<Structural Formula 5>

Here, R3 and R4 are, independently, hydrogen or a methyl group. According to claim 1,
In the backbone,
5 to 60% by weight of the first monomer, 20 to 90% by weight of the second monomer, and 5 to 30% by weight of the third monomer. delete According to claim 1,
The fourth monomer is 5 to 25 parts by weight based on 100 parts by weight of the backbone.