KR100716934B1 - Acrylate resin for photoresist - Google Patents

Abstract

The present invention relates to an acrylate resin for photoresist, in particular a) 20 to 50% by weight of unsaturated carboxylic acid; b) 20 to 40% by weight aromatic monomer; c) methacrylic ester, isotridecyl methacrylate, steryl methacrylate, isodecyl methacrylate, ethylhexyl methacrylate, ethyltriglycol methacrylate, methoxypolyethylene glycol methacrylate 3 to 15 wt% of a monomer having a low glass transition temperature imparting ability selected from the group consisting of butyl diglycol methacrylate; And d) is prepared by polymerizing 10 to 30% by weight of the acrylic monomer, the glass transition temperature is 150 ℃ or less and a weight average molecular weight of 10,000 to 40,000, the acrylate resin for a photoresist, characterized in that.

The acrylate resin of the present invention has a low glass transition temperature point of less than 150 ℃ glass transition temperature is fast dissolving rate in the solvent of the photosensitive resin composition, enabling the use of the photosensitive resin composition in the form of a dry film, excellent pattern Increased formability and flexibility significantly improve adhesion to the substrate.

Acrylate, photosensitive resin, dry film, low glass transition point acrylate

Description

Acrylate resin for photoresist

 The present invention has a low glass transition temperature point of less than 150 ℃ glass transition temperature is fast dissolving rate in the solvent of the photosensitive resin composition, enabling the use of the photosensitive resin composition in the form of a dry film, excellent pattern formation ability and increased flexibility The present invention relates to an acrylate resin for photoresist that can significantly improve adhesion to a plastic substrate.

Generally, the photosensitive resin used for pattern formation of a semiconductor display contains a polymer resin, a photosensitive compound, and a solvent. In recent years, photosensitive resins have also been used as dry film resists to form patterns.

However, the conventional photosensitive resin composition generally has a disadvantage in that the dried film is brittle because it uses an acrylate-based polymer resin having a high glass transition point, and has a problem in that adhesion to the substrate is poor. This property can be seen as a problem of deterioration in plastic substrates that have a long-term need. Accordingly, there is an urgent need for research on a photosensitive resin composition having a low glass transition point, excellent adhesion to a substrate, and particularly excellent adhesion to a plastic substrate, and an optimal polymer resin used therein.

In order to solve the problems of the prior art as described above, the present invention is included in the photosensitive resin composition to enable use as a dry film, excellent circuit line uniformity after development process (CD uniformity), and excellent resolution, development contrast In addition, an object of the present invention is to provide an acrylate resin and a photosensitive resin including the resin which can greatly improve the adhesion to the plastic substrate by increasing the flexibility.

In order to achieve the above object, the present invention

a) 20-50% by weight of unsaturated carboxylic acid;

b) 20 to 40% by weight aromatic monomer;

c) methacrylic ester of ethoxylated patty alcohol, isotridecyl methacrylate, stearyl methacrylate, isodecyl methacrylate, ethylhexyl methacrylate, ethyltriglycol methacrylate, methoxypolyethylene glycol methacrylate 3 to 15 wt% of a monomer having a low glass transition temperature imparting ability selected from the group consisting of butyl diglycol methacrylate; And

d) 10-30 wt% of acrylic monomer

It is prepared by polymerization, and provides a acrylate resin for photoresist, characterized in that the glass transition temperature is 150 ℃ or less and the weight average molecular weight is 10,000 to 40,000.

In addition, the present invention

It provides the photosensitive resin composition characterized by including the said acrylate resin.

Hereinafter, the present invention will be described in detail.

When the acrylate resin having a low glass transition point is used as a polymer resin in the photosensitive resin composition, the present inventors can use it in the form of a dry film, and the dried film is softer than the conventional photosensitive resin composition, and thus, particularly for a plastic substrate. It was confirmed that the excellent adhesive force can be applied to a large screen substrate and completed the present invention.

The acrylate polymer resin of the present invention may be prepared by polymerizing an unsaturated carboxylic acid, an aromatic monomer, a monomer having a low glass transition temperature imparting ability, and an acrylic monomer.

The unsaturated carboxylic acid is used for alkali solubility, and specifically, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, vinyl acetic acid, or an acid anhydride thereof may be used.

The unsaturated carboxylic acid is preferably included in the polymer resin of the present invention in 20 to 50% by weight, when the content is less than 20% by weight, there is a problem that the development time during the development process is long, exceeding 50% by weight If it is, it is easy to gelate at the time of polymerization, there is a problem that the degree of polymerization is difficult to control and the storage stability of the photosensitive resin composition is deteriorated.

The aromatic monomer serves to improve the chemical resistance and heat resistance of the final photosensitive resin composition.

The aromatic monomers are styrene, benzyl methacrylate, benzyl acrylate, phenyl acrylate, phenyl methacrylate, 2-nitrophenyl acrylate, 4-nitrophenyl acrylate, 2-nitrophenyl methacrylate, 4-nitrophenyl Methacrylate, 2-nitrobenzyl methacrylate, 4-nitrobenzyl methacrylate, 2-chlorophenyl acrylate, 4-chlorophenyl acrylate, 2-chlorophenyl methacrylate, or 4-chlorophenyl methacrylate Rate and the like can be used.

The aromatic monomer is preferably included in the acrylate polymer resin of the present invention 15 to 45% by weight, more preferably 20 to 40% by weight. If the content is less than 15% by weight, there is a problem in that the pattern is poorly adhered to the substrate during the development process and the pattern tearing is severe and the straightness of the formed pattern is deteriorated, so that it is difficult to implement a stable pattern. When forming the film, there is a problem that the flexibility of the film is lowered and the durability to the plastic substrate is deteriorated.

The monomer having a low glass transition temperature imparting ability lowers the glass transition point of the acrylate polymer resin of the present invention, thereby increasing the flexibility of the polymer and improving durability of the plastic.

The monomer having low glass transition temperature imparting ability is methacrylic ester of ethoxylated patty alcohol, isotridecyl methacrylate, steryl methacrylate, isodecyl methacrylate, ethylhexyl methacrylate, ethyltriglycol methacrylate Ethylene, methoxy polyethylene glycol methacrylate, butyl diglycol methacrylate, etc. can be used.

The monomer having a low glass transition temperature imparting ability is preferably included in the acrylate polymer resin of the present invention 3 to 15% by weight, more preferably 5 to 10% by weight. If the content is less than 3% by weight, there is a problem that the glass transition point of the low glass transition advantage acrylate polymer resin is easily broken, or the flexibility of the formed photosensitive resin composition is deteriorated. The tearing of the pattern is aggravated, and there is a problem that the straightness of the formed pattern is deteriorated.

The acrylic monomer acts to control the polarity of the low glass transition point acrylate polymer resin, specifically 2-hydroxyethyl (meth) acrylate, 2-hydroxyoctyl (meth) acrylate, methyl (meth) acrylic Elate, ethyl (meth) acrylate, n-butyl acrylate, etc. can be used.

The acrylic monomer is preferably included in the low glass transition point acrylate polymer resin 10 to 30% by weight, when the content is less than 10% by weight or more than 30% by weight of the low glass transition point acrylate polymer resin There exists a problem that heat resistance, dispersibility, and hydrophilicity with a developing solution fall.

Such unsaturated carboxylic acid, aromatic monomer, monomer having low glass transition temperature imparting ability, and acrylic monomer may be polymerized in a solvent having a suitable polarity to prevent gelation to prepare a final low glass transition point acrylate polymer resin. Can be. Preferably, the solvent is propylene glycol monoethyl ether acetate, ethoxy propionate, butyl acetic acid, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl Ethyl ether, cyclohexanone, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and the like can be used, and in particular, propylene glycol monoethyl ether, ethoxypropionate, or butylacetic acid is preferably used.

The acrylate polymer resin for photoresist preferably has a weight average molecular weight of 10,000 to 40,000, more preferably 15,000 to 35,000. If the weight average molecular weight is less than 10,000, there is a problem that there is no development margin during the development process, and if the weight average molecular weight exceeds 40,000, there is a problem that the development time is slowed and a residual film is generated during the development process.

It is preferable that the acrylate polymer resin of this invention is 150 degrees C or less in glass transition temperature. When the glass transition temperature exceeds 150 ℃, there is a problem in that it is not effective to impart flexibility of the final photosensitive resin composition.

In addition, the present invention includes a photosensitive resin composition comprising the acrylate resin, the photosensitive resin composition of the present invention is a photosensitive resin composition comprising a polymer resin, a photosensitive compound and a solvent, wherein the polymer resin has a glass transition temperature It is characterized by containing the said acrylate resin which is 150 degrees C or less.

Preferably, the photosensitive resin composition may include 5 to 50% by weight of an acrylate resin having a glass transition temperature of 150 ° C. or less. If the content of the acrylate resin is less than 5% by weight, the viscosity is too low to form a dry film, and if the content exceeds 50% by weight, a problem of uniform coating is difficult.

In addition, the photosensitive resin composition of the present invention includes a photosensitive compound and an organic solvent, and the photosensitive compound and the organic solvent may be used as a photosensitive compound and an organic solvent that can be used in a conventional photosensitive resin composition. Preferably, the photosensitive compound is a diazide photosensitive compound prepared by reacting polyhydroxy benzophenone with diazide compounds such as 1,2-naphthoquinone diazide and 2-diazo-1-naphthol-5-sulfonic acid. It is preferable that the compound is used, and the diazide compound is preferably included in the photoresist composition of the present invention in an amount of 1 to 20% by weight. If the content of the photosensitive compound is less than 1% by weight, there is a problem that the photosensitivity is too slow. If it exceeds 20% by weight, there is a problem that the photoresist rate is too fast and the residual film rate is lowered. In addition, the organic solvent is contained in the remaining amount in the photosensitive resin composition of the present invention, may be selected by solubility, coating properties, and the like, specifically propylene glycol monoethyl ether acetate, ethoxy propionate, butyl acetic acid, ethylene glycol monomethyl ether Acetate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3-methoxypropionate, methyl 3-ethoxypropionate, and the like can be used. In particular, propylene glycol monoethyl ether acetate, ethyl ethoxypropionate, or butyl acetic acid is preferably used.

In addition, the photosensitive resin composition of the present invention containing the above components, if necessary, additives such as conventional photopolymerization initiators, colorants, dyes, anti-scratching agents, plasticizers, adhesion promoters, speed enhancers, or surfactants are usually used as additives. By additionally included according to the content, it is of course possible to improve the performance according to the characteristics of the individual process.

The photosensitive resin composition of the present invention is excellent in the adhesive strength to the plastic substrate because the dried film is flexible compared to the existing composition, it can be manufactured in the form of a dry film applicable to a large screen substrate.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

Example 1

(Manufacture of low glass transition point acrylate polymer resin)

33% by weight of methacrylic acid, 40% by weight of benzyl methacrylate, 11% by weight of ethyltriglycol methacrylate, and 16% by weight of 2-hydroxyethyl methacrylate were polymerized in 50% by weight of propylene glycol monoethyl ether as a solvent. A low glass transition point acrylate polymer resin having a weight average molecular weight of 30,000 and a glass transition point of 102 ° C. was prepared.

Example 2

(Manufacture of low glass transition point acrylate polymer resin)

33 weight percent of methacrylic acid, 40 weight percent of benzyl methacrylate, 11 weight percent of ethyltriglycol methacrylate, and 16 weight percent of methyl methacrylate were polymerized in 50 weight percent of propylene glycol monoethyl ether as a solvent to obtain a weight average. A low glass transition point acrylate polymer resin having a molecular weight of 28,000 and a glass transition point of 145 ° C was prepared.

Example 3

(Photosensitive resin composition production)

50% by weight of the low glass transition point acrylate polymer resin prepared in Example 1, M2301 (6% by weight of bisphenol A dimethacrylate with 30 ethylene oxide), TMP (EO) ₃ TA (trimethylpropane triacryl) 12% by weight, BCIM (2,2'-bis-2-chlorophenyl-4,5,4 ', 5'-tetraphenyl-2'-1,2'-biimidazole) 4% by weight, A -DMA (tri (4-diethylaminophenyl) methane (triaryl methane-based photosensitizer, manufactured by Hodogaya Chemical) 0.4 wt%, basic dye 0.4 wt%, and propylene glycol monomethyl ether 27.2 wt% are mixed, Stirring at room temperature for 2 hours to obtain a photosensitive resin composition The resulting photosensitive resin composition was removed through a 500 mesh filter to prepare a final photosensitive resin composition.

Example 4

(Photosensitive resin composition production)

A final photosensitive resin composition was prepared in the same manner as in Example 3, except that 50 wt% of the low glass transition point acrylate polymer resin prepared in Example 2 was used.

Comparative Example 1

(Acrylate polymer resin production)

33% by weight of methacrylic acid, 40% by weight of benzyl methacrylate, 8% by weight of 2-hydroxyethyl methacrylate, and 19% by weight of methyl methacrylate were polymerized in 50% by weight of propylene glycol monoethyl ether as a solvent. An acrylate polymer resin having a weight average molecular weight of 28,000 and a glass transition point of 250 ° C. was prepared.

(Photosensitive resin composition production)

A final photosensitive resin composition was prepared in the same manner as in Example 3, except that 50 wt% of the prepared acrylate polymer resin was used.

Using the photosensitive resin composition prepared in Example 3-4 and Comparative Example 1 to prepare a dry film resist in the following manner, using a dry film resist of 40 ㎛ thickness adhesion, developability, and hole tenting strength Was evaluated.

First, after drying the photosensitive resin composition prepared in Example 3-4 and Comparative Example 1 by using an applicator on a polyethylene terephthalate film (hereinafter PET film) of 25 ㎛ so that the film thickness is 40 ㎛ and dried The photosensitive resin composition layer was formed. Then, a 20 μm polyethylene film (hereinafter referred to as PE film) was deposited on the formed photosensitive resin composition layer with a rubber roller so that no bubbles remained, thereby preparing a photosensitive dry film resist.

end. Adhesion Evaluation

After peeling the PE film of the prepared dry film resist and pressing the photosensitive resin composition layer on a glass substrate using a hot roll of 105 ℃, after exposing the entire surface at 50 mJ / ㎠, peeling off the PET film ASTM The cross-cut test was carried out according to the D3359 method, and the results are shown in Table 1 below. At this time, the adhesive force was evaluated according to the following criteria.

0B Broken into flakes, falling more than 65% 1B The tip of the cut and the lattice fall off and the area is 35-65% 2B The tip of the cut and the part of the grid fall off and the area is 15-35% 3B A small area falls off at the intersection of the cut and the area is 5-15%. 4B Falling off at the intersection of the cuts, the area of which is less than 5% 5B The edge of the cut is smooth and there is no falling off grid

TABLE 1

division Example 3 Example 4 Comparative Example 1 Adhesion 5B 5B 0B

I. Developability

After peeling off the PE film of the dry film resist prepared above, the photosensitive resin composition layer was pressed onto a glass substrate using a hot roll at 105 ° C., and then a photomask was placed on the obtained coating film, and then 200-400 nm Exposure is carried out for a certain time using an ultra-high pressure mercury lamp emitting a wavelength of about 50 mJ / cm 2 based on 365 nm, and development through a spray nozzle for a predetermined time using a KOH developer (DCD-260CF, manufactured by Dongjin Semichem Co., Ltd.). It was. The developability was evaluated through the adhesive force and the pattern shape of the developed fine pattern, and the results are shown in Table 2 below.

TABLE 2

division Example 3 Example 4 Comparative Example 1 Pattern Size 40 μm ○ ○ ○ 30 μm ○ ○ ○ 20 μm ○ ○ ○ Pattern straightness ○ ○ △ [Note] ○: Good pattern shape, adhesive strength 100% △: Normal pattern shape, adhesive strength 90% ×: Poor pattern shape, adhesive strength 80%

All. Hall tenting strength rating

Peel off the PE film of the prepared dry film resist, and the photosensitive resin composition layer is widely pressed onto a glass substrate having a 1 cm × 1 cm hole by using a hot roll of 105 ° C., and then 50 mJ / ㎠ After exposure, the PET film was peeled off and the force required until the dry film resist present on the hole was torn was measured using a tension gauge, and the results are shown in Table 3 below.

TABLE 3

division Example 3 Example 4 Comparative Example 1 Tenting strength 1.5 kg / f 1.2 kg / f 0.5 kg / f

As shown in Tables 1 to 3, the photosensitive resin composition prepared in Examples 3 and 4 using an acrylate polymer resin having a glass transition point of 150 ° C. or less according to the present invention has an adhesive strength, developability, And it was confirmed that the hole tenting strength is excellent.

According to the present invention, the acrylate resin and the photosensitive resin composition for photoresist can be used as a dry film, and have excellent CD uniformity after development, excellent resolution, development contrast, and plasticity due to increased flexibility. The adhesion to the substrate can be greatly improved.

Claims (9)

a) 20-50% by weight of unsaturated carboxylic acid; b) 20 to 40% by weight aromatic monomer; c) methacrylic ester, isotridecyl methacrylate, steryl methacrylate, isodecyl methacrylate, ethylhexyl methacrylate, ethyltriglycol methacrylate, methoxypolyethylene glycol methacrylate 3 to 15 wt% of a monomer having a low glass transition temperature imparting ability selected from the group consisting of butyl diglycol methacrylate; And d) 10-30 wt% of acrylic monomer It is prepared by polymerizing, the glass transition temperature is 150 ℃ or less and the weight average molecular weight is 10,000 to 40,000 acrylate resin, characterized in that the resin. The method of claim 1,       The unsaturated carboxylic acid is at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, vinyl acetic acid, and these anhydrides thereof. The method of claim 1, The aromatic monomers are styrene, benzyl methacrylate, benzyl acrylate, phenyl acrylate, phenyl methacrylate, 2-nitrophenyl acrylate, 4-nitrophenyl acrylate, 2-nitrophenyl methacrylate, 4-nitrophenyl Methacrylate, 2-nitrobenzyl methacrylate, 4-nitrobenzyl methacrylate, 2-chlorophenyl acrylate, 4-chlorophenyl acrylate, 2-chlorophenyl methacrylate, and 4-chlorophenyl methacrylate At least 1 type is selected from the group which consists of an acrylate resin for photoresists. delete The method of claim 1, From the group in which the said acryl monomer consists of 2-hydroxyethyl (meth) acrylate, 2-hydroxyoctyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, and n-butylacrylate. 1 or more types are selected, The acrylate resin for photoresists characterized by the above-mentioned. delete delete In the photosensitive resin composition containing a polymer resin, a photosensitive compound, and a solvent,       5 to 50% by weight of the acrylate resin for a photoresist according to claim 1, characterized in that the photosensitive resin composition. delete