TW201319736A - Photo-sensitivity resin composition - Google Patents

Abstract

A photo-sensitivity resin composition is provided that includes (A) polymer having three or more blocks, wherein the blocks include (A-1) ethylenically unsaturated monomer containing acid groups and (A-2) ethylenically unsaturated monomer except (A-1); (B) monomer having at least one ethylenically unsaturated double bond; (C) polyurethane resin oligomer having reactive acryl groups; (D) epoxy-silane copolymer; (E) organic acid anhydride; (F) photopolymerization initiator; (G) organic solvent. The (D) is represented by formula (I) or formula (II). In formula (I) and formula (II), R independently represents CH3 or OCH3 respectively; m, n, o, and p represent different repeating unit respectively.

Description

Photosensitive resin composition

The present invention relates to a photo-sensitivity resin composition, and more particularly to a photosensitive resin composition having good metal and glass adhesion and high hardness.

In order to achieve more convenience, lighter weight and more humane purposes, many information products have been converted from traditional keyboards or mice to devices that use touch devices as input. The touch device can be assembled on a wide variety of flat-panel displays, so that the flat-panel display has both a display screen and input operation information. For the current common touch devices, capacitive touch panels and resistive touch panels are the most popular.

In a general touch panel process, a photosensitive resin composition (photoresist) is generally used as a dielectric layer between metal electrodes or a protective layer covering a metal electrode. Therefore, the above-mentioned photosensitive resin composition must have a line which can be developed to protect a special pattern and a good metal or glass surface adhesion and high hardness to avoid the problem of scratching and peeling in the process. However, in general, when large-sized glass is cut, foreign matter adheres to the surface, so that ultrasonic cleaning is required in the process, and the problem of peeling off the organic photoresist (that is, the photosensitive resin composition) often occurs. Conventional photoresist as a protective layer is not ideal for adhesion to metal or glass surfaces.

The invention provides a photosensitive resin composition which has good metal and glass adhesion and high hardness, and can be peeled off by a process such as high temperature baking and ultrasonic vibration washing.

The present invention provides a photosensitive resin composition comprising: (A) a polymer having three or more blocks, (B) a monomer having at least one ethylenically unsaturated double bond, (C) a polyurethane ester resin oligomer having a reactive acrylic functional group, (D) an epoxy-decane copolymer compound, (E) an organic acid anhydride, (F) a photoinitiator, and (G) an organic solvent, wherein the above (D) ring The oxy-decane copolymer compound is a copolymer compound represented by the formula (I) or the formula (II),

In the formulae (I) and (II), R is independently CH ₃ or OCH ₃ ; m, n, o, and p are units of different repeat ratios, respectively.

The photosensitive resin composition according to the embodiment of the invention, wherein the content of the above (A) is, for example, between 10% by weight and 15% by weight based on the total weight of the photosensitive resin composition.

The photosensitive resin composition according to the embodiment of the present invention, wherein the content of the above (A-1) is, for example, 10 parts by weight based on 100 parts by weight of the total of (A-1) and (A-2) Between 90 parts by weight.

The photosensitive resin composition according to the embodiment of the present invention, wherein the content of the above (A-2) is, for example, 10 parts by weight based on 100 parts by weight of the total of (A-1) and (A-2) Between 90 parts by weight.

The photosensitive resin composition according to the embodiment of the present invention, wherein the content of the above (B) is, for example, between 5 wt% and 15 wt% based on the total weight of the photosensitive resin composition.

The photosensitive resin composition according to the embodiment of the present invention, wherein the content of the above (C) is, for example, between 1 wt% and 20 wt% based on the total weight of the photosensitive resin composition.

The photosensitive resin composition according to the embodiment of the invention, wherein the content of the above (D) is between 0.1 wt% and 10 wt% based on the total weight of the photosensitive resin composition.

The photosensitive resin composition according to the embodiment of the present invention, wherein the content of the above (E) is, for example, between 0.1 part by weight and 100 parts by weight based on 100 parts by weight of (A).

The photosensitive resin composition according to the embodiment of the present invention, wherein the content of the above (F) is, for example, between 0.1 part by weight and 100 parts by weight based on 100 parts by weight of (A).

The photosensitive resin composition according to the embodiment of the present invention, wherein the content of the above (G) is between 60% by weight and 80% by weight based on the total weight of the photosensitive resin composition.

The photosensitive resin composition according to the embodiment of the present invention, wherein the weight average molecular weight of the above (D) is from 10 k to 60 k.

A photosensitive resin composition according to an embodiment of the present invention, further comprising (H) a nanoparticle filler.

The photosensitive resin composition according to the embodiment of the invention, wherein the (H) nanoparticle filler comprises cerium oxide, titanium oxide or aluminum oxide.

The photosensitive resin composition according to the embodiment of the present invention, wherein the content of the above (H) is between 5 wt% and 20 wt% based on the total weight of the photosensitive resin composition.

Based on the above, the photosensitive resin composition of the present invention has good adhesion to metal and glass and has high hardness, and thus can be applied to a process of a touch panel. When the photosensitive resin composition of the present invention is exposed and developed, it can be a dielectric layer located between the metal electrodes, or can be a protective layer covering the metal electrode, and is not peeled off by ultrasonic shock washing.

The above described features and advantages of the present invention will be more apparent from the following description.

The photosensitive resin composition proposed by the present invention has good adhesion to metals and glass and has high hardness. Therefore, such a photosensitive resin composition can be applied to a touch panel process to form a dielectric layer between metal electrodes or a protective layer covering the metal electrodes to avoid scratching of the metal electrodes during the process. The problem of rate is able to withstand high temperature baking and ultrasonic vibration washing in the touch panel process without peeling off.

The photosensitive resin composition of the present invention comprises: (A) a polymer having three or more co-blocks, (B) a monomer having at least one ethylenically unsaturated double bond, and (C) a reactive acrylic function. a base polyurethane resin oligomer, (D) an epoxy-decane copolymer compound, (E) an organic acid anhydride, (F) a photoinitiator, and (G) an organic solvent.

In (A) a polymer having three or more co-blocks, these co-blocks include: (A-1) an acid group-containing ethylenically unsaturated monomer and (A-2) except (A-1) An ethylenically unsaturated monomer other than that. That is, (A) is at least polymerized from (A-1) and (A-2). Of course, (A) may also be formed by polymerizing (A-1) and (A-2) with other monomers. The content of (A) is, for example, between 10% by weight and 15% by weight based on the total weight of the photosensitive resin composition.

(A-1) The ethylenically unsaturated monomer having an acid group may be an unsaturated monobasic acid such as (meth)acrylic acid, crotonic acid, α-chloro(meth)acrylic acid, or (ethyl) Acrylic acid, cinnamic acid, etc.; unsaturated dibasic acids/anhydrides such as maleic acid, maleic anhydride, fumaric acid, itaconic acid ), itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, mesaconic anhydride, etc.; or trivalent or higher unsaturated Multivalent acids/anhydrides. The content of (A-1) is, for example, between 10 parts by weight and 90 parts by weight based on 100 parts by weight of the total of (A-1) and (A-2). The above (A-1) may be used singly or in combination of several kinds. The acid group contained in (A-1) contributes to an improvement in the developing characteristics of the photosensitive resin composition.

(A-2) The ethylenically unsaturated monomer other than (A-1) may be a vinyl compound containing an allyl group, such as allyl (meth)acrylate; a vinyl compound containing two acrylic groups, such as ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, propylene glycol Propylene glycol di(meth)acrylate, 2,2-dimethyl-1,3-propylene glycol di(meth)acrylate , triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tris(2-hydroxyethyl)isocyanate Tri(2-hydroxyethyl)isocyanate di(meth)acrylate, etc.; nitrileated vinyl compounds such as (meth)acrylonitrile (meth)acrylonitrile, alpha-chloro(meth)acrylonitrile (α -chloro(meth)acrylonitrile); an aromatic vinyl compound such as styrene, methyl styrene, methoxystyrene, etc.; He is a vinyl compound such as a cyclic alkyl (meth)acrylic acid such as C6 to C12. (A-2) is preferably dicyclopentanyl methacrylate, styrene, iso-octylacrylate, allylmethacrylate, methacrylonitrile ( Methacrylonitrile), 2,2-dimethyl-1,3-propane glycoldiacrylate. When (A-2) is styrene, the heat resistance and chemical resistance of the photosensitive resin composition of the present invention can be further improved. The content of (A-2) is, for example, between 10 parts by weight and 90 parts by weight based on 100 parts by weight of the total of (A-1) and (A-2). The above (A-2) may be used singly or in combination of several kinds.

The weight average molecular weight (Mw) obtained by (A) polystyrene conversion by gel permeation chromatography is preferably between 2 × 10 ³ and 1 × 10 ⁵ , more preferably between 5 × 10 ³ and 5 × 10 Between ⁴ . When the weight average molecular weight of (A) is less than 2×10 ³ , there may be a problem that the formed dielectric layer or the protective layer may cause pattern inaccuracy, and the thickness of the dielectric layer or the protective layer may be generated after a high temperature process. The problem of thinning means that the pattern shape and heat resistance of the dielectric layer or the protective layer are deteriorated. When the weight average molecular weight of (A) is more than 1 × 10 ⁵ , there is a possibility that the sensitivity of the photosensitive resin composition is lowered, and the accuracy of the dielectric layer or the protective layer pattern is also lowered.

(B) The monomer having at least one ethylenically unsaturated double bond may be ethylene glycol di(meth)acrylate; having 2 to 14 ethylene oxide groups Polyethylene glycol di(meth)acrylate; trimethylol propane di(meth)acrylate; trimethylol propane tri (meth)acrylate); pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate; with 2 to 14 epoxy Propylene propylene propylene glycol (divalent erythritol penta (meth) acrylate); dipentaerythritol penta (meth) acrylate; dipentaerythritol hexa (dipentaerythritol hexa (dipentaerythritol hexa methacrylate) Meth)acrylate, DPHA); trimethylolpropanetriglycidylether acrylic acid additive; bisphenol A diglycidyl ether acrylic acid Bisphenol A diglycidylether acrylic acid additives; phthalate diesters of β-hydroxyethyl (meth)acrylate; toluene dihydrogenate additive (toluene diisocyanate) (for example, β-hydroxyethyl (meth)acrylate; a monomer having an ethylenically unsaturated bond, wherein the ethylenically unsaturated bond is selected from the group consisting of ditrihydroxyl Ditrimethylol propanetetraacrylate, tris(2-acryloxyethyl)isocyanurate, ethoxylated pentaerylthritol-tetraacrylate (EO 4 mol), pentaerythrit0ltetraacrylate (EO 35 mol), ethoxylated trimethylolpropane-triacrylate (EO 9 mol), ethoxylate-containing Trimethylolpropane triacrylate (EO 3 mol), propxylated pentaerythritoltetraacrylate (PO 4 mol), nonaethylene glycol diacrylate ( Nonaethylene glycol diacrylate), a group consisting of dipentaerythritol hexa-acrylate-modified caprolactone and trimethylolpropane propoxylate triacrylate. The content of (B) is, for example, between 5 wt% and 15 wt%, preferably between 10 wt% and 13 wt%, based on the total weight of the photosensitive resin composition. The above (B) can be used singly or in combination of several kinds, whereby the hardness of the photosensitive resin composition of the present invention can be improved.

(C) A polyurethane resin oligomer having a reactive acrylic functional group having an acid value (mgKOH/g) of from 0 to 100. The above (C) may be a general commercial product, and for example, KAYARAD DPHA-40H (sold by Nippon Kayaku Co., Ltd.); U-4HA, U-6HA, U-6LPA, U-15HA, UA-32P , U-324A, U-4H, U-6H (manufactured by Shin-Nakamura Chemical Co., Ltd.); UN-9000H, UN-3320HA, UN-3320HB, UN-3320HC, UN-901, UN-1200TPK, UN-904 (made by Kokusai Industrial Co., Ltd.). The polyurethane resin segment of the polyurethane resin oligomer is formed by polymerizing an isocyanate and a hydroxy compound. The isocyanate may be an aromatic diisocyanate such as 2,4-tolylene diisocyanate or 2,6-tolylene diisocyanate. , xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, 4,4' -4,4'-diphenylmethane diisocyanate (MDI), 2,4'-diphenylmethane diisocyanate, 4,4' -4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate ), 2,2'-phenylpropane-4,4'-diisocyanate (2,2'-diphenylpropane-4,4'-diisocyanate), 3,3'-dimethyldipropylmethyl -4,4'-diisocyanate (4,4'-diphenylpropane diisocyanate), 4,4'-diphenylpropane diisocyanate , m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate ), naphthalene-1,5-diiso Cyanate (naphthylene-1,5-diisocyanate), 3,3'-dialkoxyxylene-4,4'-diisocyanate (3,3'-dimethoxydiphenyl-4,4'-diisocyanate) Aliphatic diisocyanates, such as tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), lysine diisocyanate Lysine diisocyanate; alicyclic diisocyanates, such as isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene Hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylene diisocyanate. The above isocyanate is for illustrative purposes only, but is not limited thereto, and the isocyanate used to polymerize the polyurethane resin segment may be used in combination of one or more kinds. The hydroxy compound used to polymerize the polyurethane resin segment may be a diol such as ethylene glycol, propylene glycol, tetramethylene glycol, 1,5-pentanediol ( 1,5-pentanediol), 1,6-hexanediol, 1,10-decanediol, 1,4-dicyclohexenol (1,4 -dihydroxycyclohexane), 1,4-dihydroxymethylcyclohexane, diethylene glycol, triethylene glycol; amino alcohol; polymer polyol . The above hydroxy compound is for illustrative purposes only, but is not limited thereto, and the hydroxy compound used to polymerize the polyurethane resin segment may also be used in combination of one or more. The content of (C) is between 1 wt% and 20 wt%, preferably between 3 wt% and 15 wt%, more preferably between 5 wt% and 10 wt%, based on the total weight of the photosensitive resin composition. %between. The above (C) may be used singly or in combination of several kinds. (C) The photosensitive resin composition of the present invention can be made flexible so as to avoid too much (B) and embrittle the material.

(D) The epoxy-decane copolymer compound is a copolymer compound represented by the following formula (I) or formula (II).

In the formulae (I) and (II), R is independently CH ₃ or OCH ₃ ; m, n, o, and p are units of different repeat ratios, respectively.

The above (D) may be an oligomer produced by Arakawa Chemical Co., Ltd. (for example, trade name E-102B). The content of (D) is between 0.1 wt% and 10 wt% based on the total weight of the photosensitive resin composition. (D) has a weight average molecular weight of 10k to 60k. (D) itself will be self-sol-gel, such that CH _{3 in the} (D) bond with Si-O is broken, and Si-O losing the CH ₃ bond will be associated with the surrounding Si. -O is bonded to each other to form a crosslinked structure. This crosslinked structure can improve the adhesion between the photosensitive resin composition of the present invention and metal or glass, and the hardness of the photosensitive resin composition of the present invention can be improved because the number of bonds of Si-O is increased.

(E) The organic acid anhydride may be maleic anhydride (MA), itaconic anhydride, tetrahydro-phthalic anhydride, citraconic anhydride, mesaconic anhydride ( Mesaconic anhydride) and so on. The content of (E) is, for example, between 0.1 part by weight and 100 parts by weight based on 100 parts by weight of (A). The above (E) may be used singly or in combination of several kinds. (E) The pattern formed by the photosensitive resin composition of the present invention can be refined.

(F) a photoinitiator which, when irradiated with energy, produces an active material which initiates a crosslinking reaction (for example, a radical, a cation or an anion, etc.). The photoinitiator may be a phosphine oxide compound, Acetophenone, benzoin, benzophenone carbonyl compound, aminocarbonyl compound, anthraquinone triazine compound An oxime-based compound, an amine-based compound, an alkoxyantharcene-based compound, or a thioxanthone-based compound. The content of (F) is, for example, between 0.1 part by weight and 100 parts by weight based on 100 parts by weight of (A). The above (F) may be used singly or in combination of several to obtain a higher photosensitive speed.

(G) The organic solvent may be benzene, toluene, xylene, methanol, ethanol, ethylene glycol monopropyl ether, diethylene glycol dimethyl Diethylene glycol dimethyl ether, diethylene glycol methyl ether, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate ), tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate ), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate (PGMEA) ), propylene glycol ethyl ether acetate, propylene glycol propyl ether Acetate), methyl isobutyl ketone, methyl ether ketone, ketone, cyclohexanone, dimethyl formamide (DMF), N, N N-N-dimethylacetamide (DMAc), N-Methyl pyrrolidone (NMP), γ-butyrolactone. The content of (G) is, for example, between 60% by weight and 80% by weight based on the total weight of the photosensitive resin composition. The above (G) may be used singly or in combination of several kinds.

Further, the photosensitive resin composition of the present invention may further comprise (H) a nanoparticle filler. (H) Nanoparticle fillers include nanoparticles such as cerium oxide, titanium oxide or aluminum oxide. The nanoparticles in (H) will react with (D) above, and these nanoparticles will be embedded in the crosslinked structure in (D) above or bonded to the crosslinked structure in (D) above, thereby causing The photosensitive resin composition of the present invention has better adhesion and stability. Further, the nanoparticle in (H) itself is hard, and the hardness of the photosensitive resin composition of the present invention can be improved, but the nanoparticle itself is relatively opaque and can be appropriately added as needed. The content of (H) is, for example, between 5 wt% and 20 wt%, based on the total weight of the photosensitive resin composition.

As described above, since the photosensitive resin composition of the present invention has good adhesion to metal and glass and has high hardness, it can be applied to a process of a touch panel. When the photosensitive resin composition of the present invention is exposed and developed, it may be formed as a dielectric layer between the metal electrodes, or may be formed as a protective layer covering the metal electrode to prevent the metal electrode from being scratched during the process. Causes low yield problems.

[Experimental example]

The photosensitive resin composition of the present invention will be described below by way of experimental examples.

(A) A polymer having three or more co-blocks was prepared as follows: 95.673 kg of ethyl 3-ethoxypropionate was added to the reaction vessel as a solvent. Then, nitrogen gas was passed through and stirred and heated to 130 °C. Next, 24.451 kg of methacrylic acid, 42.614 kg of benzyl methacrylate, 42.443 kg of isobornyl methacrylate and 2.547 kg of tert-butyl peroxybenzoate ( T-butyl perbenzoate) Stir well and drip into a reaction vessel at 130 ° C (dropping time of about 6 hours). Thereafter, 72.195 kg of ethyl 3-ethoxypropionate was added and the temperature of the autoclave was lowered back to 50 °C. Then, supply of nitrogen gas was stopped, and 6.636 kg of glycidyl methacrylate, 0.716 kg of dimethyl amino ethanol (catalyst) was added, and the reaction was stirred in the air for 4 hours to 6 hours. The obtained resin solution product had a solid content of 41.4 wt.%, a viscosity of 2650 cps/25 ° C, an acidity of 88.3 mgKOH/g, and a weight average molecular weight of 12,000.

In the photosensitive resin compositions of Experimental Example 1 - Experimental Example 3 and Comparative Example 1 - Comparative Example 3, the components other than the above (A) are shown in Table 1.

The adhesion of the photosensitive resin composition of the present invention after ultrasonic vibration washing will be examined below.

The photosensitive resin compositions of the above Experimental Examples 1 to 3 and Comparative Examples 1 to 3 were applied onto ITO glass at a number of revolutions of 350 rpm, and then left to stand at room temperature for about 120 sec. It was then placed on a hot plate and pre-baked at about 100 ° C for 90 sec. After the temperature is returned, the exposure step is performed, and the development step is performed. Then, a thermal hardening process is performed at a high temperature to form a photoresist.

Only the photoresist formed in Experimental Example 1, Experimental Example 3, and Comparative Example 2 was subjected to ultrasonic vibration washing. The ultrasonic cleaner has a power of 1200W and a vibration frequency of 40kHz. Finally, the photoresists formed in Experimental Examples 1 to 3 and Comparative Examples 1 to 3 were subjected to a pencil hardness test and a Baige adhesion test. The pencil hardness test was performed with a Japanese Mitsubishi pencil, and the adhesion test was performed with 3M tape. The test results and the above experimental conditions are shown in Table 1.

As is clear from Table 1, the photosensitive resin compositions of the present invention (Experimental Example 1 and Experimental Example 3) have good adhesion after ultrasonic vibration washing as compared with the general photosensitive resin composition (Comparative Example 2). And high hardness.

As is clear from Table 1, the photosensitive resin composition of the present invention (Experimental Example 2) has better adhesion than (D) because it is contained in a general photosensitive resin composition (Comparative Example 3).

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.

Claims (14)

A photosensitive resin composition comprising: (A) a polymer having three or more co-blocks, the co-blocks comprising: (A-1) an ethylenically unsaturated monomer having an acid group; and (A) - 2) an ethylenically unsaturated monomer other than (A-1); (B) a monomer having at least one ethylenically unsaturated double bond; (C) a polyurethane resin oligomer having a reactive acrylic functional group (D) an epoxy-decane copolymer compound; (E) an organic acid anhydride; (F) a photoinitiator; and (G) an organic solvent, wherein the (D) epoxy-decane copolymer compound is of the formula (I) Or a copolymer compound represented by formula (II), In the formulae (I) and (II), R is independently CH ₃ or OCH ₃ ; m, n, o, and p are units of different repeat ratios, respectively. The photosensitive resin composition according to claim 1, wherein the content of the (A) is between 10% by weight and 15% by weight based on the total weight of the photosensitive resin composition. The photosensitive resin composition according to claim 1, wherein the content of the (A-1) is 100 parts by weight based on the total of the (A-1) and the (A-2) Between 10 parts by weight and 90 parts by weight. The photosensitive resin composition according to claim 1, wherein the content of the (A-2) is 100 parts by weight based on the total of the (A-1) and the (A-2) Between 10 parts by weight and 90 parts by weight. The photosensitive resin composition according to claim 1, wherein the content of the (B) is between 5 wt% and 15 wt% based on the total weight of the photosensitive resin composition. The photosensitive resin composition according to claim 1, wherein the content of the (C) is between 1 wt% and 20 wt% based on the total weight of the photosensitive resin composition. The photosensitive resin composition according to claim 1, wherein the content of the (D) is between 0.1 wt% and 10 wt% based on the total weight of the photosensitive resin composition. The photosensitive resin composition according to claim 1, wherein the content of the (E) is from 0.1 part by weight to 100 parts by weight based on 100 parts by weight of the (A). The photosensitive resin composition according to claim 1, wherein the content of the (F) is from 0.1 part by weight to 100 parts by weight based on 100 parts by weight of the (A). The photosensitive resin composition according to claim 1, wherein the content of the (G) is between 60% by weight and 80% by weight based on the total weight of the photosensitive resin composition. The photosensitive resin composition according to claim 1, wherein the weight average molecular weight of the (D) is from 10 k to 60 k. The photosensitive resin composition according to claim 1, further comprising (H) a nanoparticle filler. The photosensitive resin composition according to claim 12, wherein the (H) nanoparticle filler comprises cerium oxide, titanium oxide or aluminum oxide. The photosensitive resin composition according to claim 12, wherein the content of the (H) is between 5 wt% and 20 wt% based on the total weight of the photosensitive resin composition.