Photosensitive resin composition, dry film, cured product, and printed circuit board

Abstract

An embodiment of the present invention relates to a photosensitive resin composition comprising (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, and (C) an inorganic filler, wherein the photopolymerization initiator (B) comprises at least one moiety represented by chemical formula 1. In the photosensitive resin composition, a solder resist layer formed through a combination of four components shows a low moisture absorption rate and moisture permeability and undergoes less ion migration even after HAST evaluation. In addition, the composition has excellent thermal stability and therefore generates less outgas. Due to these characteristics, the photosensitive resin composition of the present invention can exhibit an excellent effect as a solder resist.

Description

Photosensitive resin composition, dry film, cured product, and printed wiring board

[0001] The present invention relates to a photosensitive resin composition, a dry film, a cured product, and a printed wiring board, and more particularly, the dry film has a photosensitive resin layer formed by applying and drying the photosensitive resin composition on a first film, the cured product is obtained by curing the photosensitive resin composition or the photosensitive resin layer of the dry film, and the printed wiring board includes the cured product.

[0002] Typically, copper foil is etched along circuit wiring on a laminated board to form electrodes, and electronic components are then placed in their designated locations and soldered. A solder resist film is used as a protective film for the circuit when soldering electronic components to these printed wiring boards. The solder resist film not only prevents solder from adhering to unnecessary areas during soldering, but also protects the circuit conductors from direct exposure to air and corrosion by oxygen or moisture. Preventing oxidation or corrosion of the electrodes due to oxygen or moisture is crucial, as this can reduce the reliability of electronic devices. For this reason, it is crucial to increase the adhesion of the solder resist film and reduce its hygroscopicity and moisture permeability. Low hygroscopicity and moisture permeability of the solder resist film result in superior HAST resistance and less ion migration, preventing electrode oxidation and corrosion, thereby maintaining excellent reliability in electronic devices.

[0003] Meanwhile, the use of computer monitors, laptops, televisions, automotive displays and headlamps, mini LED displays, backlights for LED displays, and also as light sources for lighting fixtures, as well as PCBs, where low-power light-emitting diodes (LEDs) are directly mounted on printed wiring boards with a white solder resist film, is increasing. Furthermore, they are also used in colored solder resist films of various colors (blue, red, green, yellow, and black) on the PCBs or component substrates of electronic devices such as digital watches, electronic wristwatches, earphones, smartphones, cameras, and micro LED displays. It is also necessary for the solder resist films of these electronic devices to have low moisture absorption and high thermal stability.

[0004] From this perspective, there is a need for a method for manufacturing a dry film and a printed wiring board including a solder resist layer of a composition that exhibits low moisture absorption and low moisture permeability, while exhibiting excellent HAST resistance and low ion migration, by simply changing the composition without adding a separate sheet or film on top of the solder resist film.

[0005] [Prior Art Literature]

[0006] [Patent Document]

[0007] (Patent Document 1) Korean Patent Publication No. 10-2022-0086524

[0008] (Patent Document 2) Korean Patent Publication No. 10-2024-0147558

[0009] The purpose is to provide a photosensitive resin composition having excellent absorbance in the UV range (e.g., 350 to 430 nm) and thus excellent surface curing, and thus capable of forming a solder resist having a high acrylate reaction rate and low moisture absorption rate and moisture permeability.

[0010] In addition, the present invention provides a photosensitive resin composition capable of forming a solder resist having a high reflectivity and low ion migration even when subjected to a long-term reliability evaluation for a long period of time (e.g., 1,000 hours) in a harsh environment with high temperature and humidity.

[0011] In addition, the purpose is to provide a photosensitive resin composition having excellent thermal stability and capable of reducing the generation of outgas.

[0012] In addition, the present invention provides a dry film, a cured product, a printed wiring board, and a laminate using the photosensitive resin composition.

[0013] The present invention provides a white and / or colored solder resist composition, and more particularly, a white and / or colored solder resist composition having low moisture absorption and moisture permeability, excellent pencil hardness, low ion migration after HAST evaluation, and low outgassing content, a solder resist layer obtained therefrom, a dry film and a printed wiring board including the same, and a method for manufacturing the same.

[0014] One embodiment of the present invention relates to a photosensitive resin composition.

[0015] In one aspect, the photosensitive resin composition comprises (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, and (C) an inorganic filler, wherein the (B) photopolymerization initiator comprises at least one moiety represented by the following chemical formula 1.

[0016] <Chemical Formula 1>

[0017]

[0018] In the above chemical formula 1, R 1is hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted non-aromatic cyclic group or aromatic group having 6 to 20 carbon atoms, and R a is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and the substituent of the substituted alkyl group having 1 to 10 carbon atoms, the substituted non-aromatic cyclic group having 6 to 20 carbon atoms, or the aromatic group is an alkyl group having 1 to 10 carbon atoms, and * is a bonding site with an adjacent atom.

[0019] In one aspect, the photopolymerization initiator (B) may include one or more moieties represented by the following chemical formula 1A.

[0020] <Chemical Formula 1A>

[0021]

[0022] R a and R b is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and the substituent of the substituted alkyl group having 1 to 10 carbon atoms is an alkyl group having 1 to 10 carbon atoms, and * is a bonding site with an adjacent atom.

[0023] In one aspect, the photopolymerization initiator (B) may include one or more moieties represented by the following chemical formula 1-1.

[0024] <Chemical Formula 1-1>

[0025]

[0026] * is a bonding site with a neighboring atom.

[0027] In one aspect, the above (B) photopolymerization initiator is in a solid state at room temperature (25°C) and has a weight average molecular weight (M w ) can range from 350 to 900 g / mol.

[0028] In one aspect, the photopolymerization initiator (B) may have a thermal decomposition temperature of 240°C or higher.

[0029] In one aspect, the photopolymerization initiator (B) may be represented by the following chemical formula 2.

[0030] <Chemical Formula 2>

[0031]

[0032] In one aspect, the photopolymerization initiator (B) may be represented by any one of the following chemical formulas 3 to 5.

[0033] <Chemical Formula 3>

[0034]

[0035] <Chemical Formula 4>

[0036]

[0037] <Chemical Formula 5>

[0038]

[0039] In one aspect, the photosensitive resin composition may further include at least one selected from the group consisting of an oxime photopolymerization initiator, an epoxy resin, an acrylic resin, a thermal curing catalyst, a dispersant, and a colorant.

[0040] In one aspect, the thermosetting catalyst may be one or more selected from the group consisting of imidazole, melamine, and dicyandiamide, or a derivative thereof.

[0041] In one aspect, the colorant may be at least one selected from the group consisting of a white pigment, a black pigment, a blue pigment, and a green pigment.

[0042] In one aspect, the content of the photopolymerization initiator (B) may be 0.06 to 20 wt% based on the total weight of the composition.

[0043] In one aspect, when the photosensitive resin composition is cured to a thickness of 60 μm, the reflectance of the cured product may be 90% or more at 450 nm when the reflectance is measured using a spectrophotometer.

[0044] In one aspect, the moisture absorption rate (water absorption rate) of the cured product obtained by curing the photosensitive resin composition may be 5% or less as measured by the method of ASTM D570.

[0045] In one aspect, the moisture vapor transmission rate (WVTR) measured by the ASTM F1249 method for the cured product of the photosensitive resin composition was 33 (g / m 2 ·day) may be less than or equal to.

[0046] Another embodiment of the present invention relates to a dry film having a photosensitive resin layer formed by applying and drying the photosensitive resin composition described above on a first film.

[0047] Another embodiment of the present invention relates to a cured product obtained by curing the photosensitive resin layer of the photosensitive resin composition described above or a dry film obtained through the same.

[0048] Another embodiment of the present invention relates to a printed wiring board comprising the above-described cured product as a solder resist.

[0049] The photosensitive resin composition according to one embodiment of the present invention has excellent absorbance in the UV region (e.g., 350 to 430 nm) and thus has excellent surface curing, and thus can form a solder resist having a high acrylate reaction rate and low moisture absorption rate and moisture permeability.

[0050] In addition, the photosensitive resin composition according to one embodiment of the present invention can form a solder resist that maintains a high reflectivity and exhibits low ion migration even when subjected to long-term reliability evaluation for a long period of time (e.g., 1,000 hours) in a harsh environment with high temperature and high humidity.

[0051] In addition, the photosensitive resin composition according to one embodiment of the present invention has excellent thermal stability and can reduce the generation of outgas.

[0052] In addition, the present invention can provide a dry film, a cured product, and a printed wiring board using the photosensitive resin composition.

[0053] Figure 1 is a graph showing the absorbance at 350 to 430 nm of the TMO initiator used in the examples and the TPO, TPO-L, and Omnipol TP initiators used in the comparative examples.

[0054] Figures 2a and 2b are graphs showing the moisture permeability of dry films using the photosensitive resin compositions of Example 3 and Comparative Example 1.

[0055] Figure 3 is a photograph showing ion migration after HAST evaluation of a dry film using the photosensitive resin composition of Example 3 and Comparative Example 1.

[0056] Various embodiments of the present invention are described below.

[0057] [Photosensitive resin composition]

[0058] One embodiment of the present invention relates to a photosensitive resin composition comprising (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, and (C) an inorganic filler, wherein the (B) photopolymerization initiator comprises at least one moiety represented by the following chemical formula 1.

[0059] <Chemical Formula 1>

[0060]

[0061] In the above chemical formula 1, R 1 is hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted non-aromatic cyclic group or aromatic group having 6 to 20 carbon atoms, and R bis a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and the substituent of the substituted alkyl group having 1 to 10 carbon atoms, the substituted non-aromatic cyclic group having 6 to 20 carbon atoms, or the aromatic group is an alkyl group having 1 to 10 carbon atoms, and * is a bonding site with an adjacent atom.

[0062] The photosensitive resin composition has excellent absorbance in the UV range (e.g., 350 to 430 nm), thereby enabling better surface curing, and thus forming a solder resist with a high acrylate reaction rate and low hygroscopicity and moisture permeability. Furthermore, even when subjected to long-term reliability evaluation in a harsh, high-temperature, high-humidity environment for a long period of time (e.g., 1,000 hours), it can form a solder resist that maintains a high reflectivity and exhibits minimal ion migration. Furthermore, the composition has excellent thermal stability, thereby reducing outgassing.

[0063] For example, the photosensitive resin composition may be a composition that is cured to form a white or colored solder resist.

[0064] Below, each component of the photosensitive resin composition is described in detail.

[0065] [(A) Carboxyl group-containing resin]

[0066] In a photosensitive resin composition according to one embodiment of the present invention, (A) the carboxyl group-containing resin (hereinafter, “resin (A)”) may be a resin that exhibits electrical insulation properties by being cured by irradiation with active energy rays.

[0067] Resin (A) contains carboxyl groups, enabling alkaline development. Furthermore, the combination of the inorganic filler (B), described below, enables high reflectivity, minimizes reflectivity reduction after the reflow process, and minimizes reflectivity reduction after a 3,000-hour blue light test. Therefore, compositions containing resin (A) exhibit minimal reflectivity reduction.

[0068] For example, the resin (A) may contain an unsaturated double bond. By containing an unsaturated double bond, the resin (A) is capable of radical curing by ultraviolet rays, electron beams, or heat.

[0069] The resin (A) is not particularly limited as long as it contains a carboxyl group, but may be, for example, a photosensitive carboxyl group-containing resin having at least one photosensitive unsaturated double bond therein or a carboxyl group-containing resin having no photosensitive unsaturated double bond.

[0070] For example, as resin (A), the resins listed below can be suitably used:

[0071] (1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid and a compound having an unsaturated double bond;

[0072] (2) A photosensitive carboxyl group-containing resin obtained by reacting a carboxyl group-containing (meth)acrylic copolymer resin with a compound having an oxirane ring and an ethylenically unsaturated group in one molecule.

[0073] (3) A photosensitive carboxyl group-containing resin obtained by reacting a copolymer of a compound having one epoxy group and an unsaturated double bond in each molecule and a compound having an unsaturated double bond with an unsaturated monocarboxylic acid, and reacting the secondary hydroxyl group-saturated or unsaturated polybasic acid anhydride produced by the reaction.

[0074] (4) A resin containing photosensitive hydroxyl and carboxyl groups, obtained by reacting a saturated or unsaturated polybasic acid anhydride with a hydroxyl group-containing polymer, and then reacting a compound having one epoxy group and one unsaturated double bond in each of the carboxylic acid molecules produced by the reaction.

[0075] For example, the resin (A) may be a (a) carboxyl group-containing (meth)acrylic copolymer resin, which is a resin containing a photosensitive carboxyl group of (2), and (b) a copolymer resin having a carboxyl group obtained by the reaction of a compound having an oxirane ring and an ethylenically unsaturated group in one molecule.

[0076] For example, (a) a carboxyl group-containing (meth)acrylic copolymer resin can be obtained by copolymerizing a (meth)acrylic acid ester and a compound having one unsaturated group and at least one carboxyl group per molecule, but is not limited thereto. The (meth)acrylic acid esters constituting the copolymer resin (a) include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, and hexyl (meth)acrylate, hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and caprolactone-modified 2-hydroxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, and isooctyloxyethylene glycol (meth)acrylate, Examples of glycol-modified (meth)acrylates include phenoxytriethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate. These may be used alone, or two or more types may be mixed and used. In addition, in this specification, (meth)acrylate is a general term for acrylate and methacrylate, and the same applies to other similar expressions.

[0077] In addition, compounds having one unsaturated group and at least one carboxyl group in one molecule include acrylic acid, methacrylic acid, modified unsaturated monocarboxylic acids with an extended chain between the unsaturated group and the carboxylic acid, such as β-carboxyethyl (meth)acrylate, 2-acryloyloxyethyl cohaxic acid, 2-acryloyloxyethyl hexahydrophthalic acid, unsaturated monocarboxylic acids having an ester bond through lactone modification, modified unsaturated monocarboxylic acids having an ether bond, and maleic acid, which contain two or more carboxyl groups in the molecule. These may be used alone or as a mixture of two or more.

[0078] (b) The compound having an oxirane ring and an ethylenically unsaturated group in one molecule may be any compound having an oxirane ring and an ethylenically unsaturated group in one molecule, and examples thereof include glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxycyclohexylethyl (meth)acrylate, 3,4-epoxycyclohexylbutyl (meth)acrylate, and 3,4-epoxycyclohexylmethylaminoacrylate. These may be used alone, or two or more types may be mixed and used. For example, (b) the compound having an oxirane ring and an ethylenically unsaturated group in one molecule may be 3,4-epoxycyclohexylmethyl (meth)acrylate.

[0079] For example, the acid value of the resin (A) may be 30 to 200 mgKOH / g. When the acid value of the resin (A) is 30 mgKOH / g or more, the unexposed portion of the solder resist composition film in a weakly alkaline aqueous solution can be easily removed. When the acid value of the resin (A) is 200 mgKOH / g or less, the water resistance and electrical properties of the cured film can be improved.

[0080] For example, the weight average molecular weight of the resin (A) may be 5,000 to 100,000 g / mol. When the weight average molecular weight of the resin (A) is 5,000 g / mol or more, the deterioration of the touch-drying property of the solder resist composition film can be suppressed. When the weight average molecular weight of the resin (A) is 100,000 g / mol or less, the deterioration of the developability and storage stability of the solder resist composition can be suppressed.

[0081] In the photosensitive resin composition of the present invention, the content of the resin (A) may be 5 to 50 wt%, 10 to 45 wt%, or 12 to 43 wt% based on the total composition. The composition includes a solid content and a solvent. The content of the resin (A) may be calculated based on the solid content conversion standard.

[0082] When the content of resin (A) is within the above range, the yellowing resistance is excellent, high reflectivity can be achieved, a solder resist film can be formed well, excellent pencil hardness and adhesion can be exhibited, and the touch dryness of the film and undercutting can be suppressed.

[0083] [(B) Photopolymerization initiator]

[0084] A photosensitive resin composition according to one embodiment of the present invention may include a (B) photopolymerization initiator including at least one moiety represented by the following chemical formula 1.

[0085] <Chemical Formula 1>

[0086]

[0087] In the above chemical formula 1, R 1 is hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; or a substituted or unsubstituted non-aromatic cyclic group or aromatic group having 6 to 20 carbon atoms, and R ais a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and the substituent of the substituted alkyl group having 1 to 10 carbon atoms, the substituted non-aromatic cyclic group having 6 to 20 carbon atoms, or the aromatic group is an alkyl group having 1 to 10 carbon atoms, and * is a bonding site with an adjacent atom.

[0088] The alkyl group having 1 to 10 carbon atoms may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl, and the non-aromatic cyclic group or aromatic group having 6 to 20 carbon atoms may be benzene, toluene, ethylbenzene, propylbenzene, butylbenzene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, nonylbenzene, decylbenzene, naphthalene, or an anthracene group, and R a can be substituted at any of the ortho, meta, or para positions.

[0089] In the case of 2,4,6-trimethylbenzoyldiphenyl phosphine oxide (TPO), which is widely used as a conventional photopolymerization initiator, a large amount of outgas is generated during the curing process, and these outgases diffuse into the silicone encapsulant layer or protective film, causing yellowing of the silicone encapsulant, reducing reflectivity and making curing of the silicone encapsulant difficult. This caused problems with the long-term reliability of the product.

[0090] In addition, in the case of TPO, TPO-L, etc., the UV absorbance is low, so a large amount of exposure is required, which leads to a long working time, and the reaction rate of acrylate is low due to the low absorbance, which leads to poor surface curing, high moisture absorption, and problems of good moisture penetration.

[0091] In addition, TPO, TPO-L, etc. have low thermal stability, so they are easily decomposed by heat, generating a lot of outgassing, which causes problems such as yellowing of the sealing layer.

[0092] On the other hand, the photosensitive resin composition according to one embodiment of the present invention has a structure in which a methyl group is substituted for a phenyl group bonded to phosphorus (P) as a photopolymerization initiator, thereby having a more hydrophobic property and high thermal stability and UV absorbance, thereby achieving excellent surface curing and low outgassing.

[0093] In addition, by using the photopolymerization initiator (B) of the present invention described above, work is possible even with a low exposure dose through high absorbance, so that the yield is increased by reducing the work time, the cost is reduced, the reflectance can be increased, the power consumption due to the decrease in reflectance can be prevented, the outgassing content of the photopolymerization initiator is very low without using a protective film for removing the photopolymerization initiator, etc., the curing degree of silicone is greatly increased, the long-term reliability is improved, the moisture absorption rate is low, and the moisture permeability is low, so that excellent HAST resistance and reflectance after the HAST test can be exhibited. In addition, the decrease in reflectance under high temperature / high humidity conditions can be suppressed.

[0094] For example, the photopolymerization initiator (B) may include one or more moieties represented by the following chemical formula 1A.

[0095] <Chemical Formula 1A>

[0096]

[0097] R a and R b is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, the substituent of the substituted alkyl group having 1 to 10 carbon atoms is an alkyl group having 1 to 10 carbon atoms, and * is a bonding site with an adjacent atom.

[0098] The above R a and R b may be identical or different from each other. The above R a and R bcan be substituted independently of each other at any of the ortho, meta, or para positions.

[0099] For example, the photopolymerization initiator (B) may include one or more moieties represented by the following chemical formula 1-1.

[0100] <Chemical Formula 1-1>

[0101]

[0102] * is a bonding site with a neighboring atom.

[0103] In the above chemical formula 1-1, two methyl groups (-CH3) can be independently substituted at any one of the ortho, meta, or para positions.

[0104] For example, the above (B) photopolymerization initiator is in a solid state at room temperature (25°C) and has a weight average molecular weight (M w ) can range from 350 to 900 g / mol.

[0105] For example, the photopolymerization initiator (B) above may have a thermal decomposition temperature of 240°C or higher. Since the thermal decomposition temperature of the photopolymerization initiator (B) satisfies the above range, it has excellent thermal stability, and is relatively less decomposed even at high temperatures, so the outgas content is lower compared to conventional photopolymerization initiators.

[0106] For example, the photopolymerization initiator (B) may be represented by the following chemical formula 2.

[0107] <Chemical Formula 2>

[0108]

[0109] For example, the photopolymerization initiator (B) may be represented by any one of the following chemical formulas 3 to 5.

[0110] <Chemical Formula 3>

[0111]

[0112] <Chemical Formula 4>

[0113]

[0114] <Chemical Formula 5>

[0115]

[0116] For example, in addition to the above (B) photopolymerization initiator, it may further include one or more selected from the group consisting of benzoin and its alkyl ethers, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, α-aminoacetophenones, acylphosphine oxides, acylphosphinates, and oxime esters. Examples of the oxime ester photopolymerization initiator include commercially available products such as CGI-325 manufactured by BASF Japan, Irgacure (registered trademark) OXE01, Irgacure OXE02, N-1919 manufactured by Adeka Corporation, and Adeka Acles (registered trademark) NCI-831.

[0117] In the photosensitive resin composition of the present invention, the content of the (B) photopolymerization initiator may be 0.01 to 25 wt%, 0.01 to 20 wt%, or 0.01 to 18 wt% based on the entire composition. By including the (B) photopolymerization initiator in this range, the photoreaction rate on copper is excellent, so that the photocurability is sufficient, the curability of the coating film is improved, and the coating film properties such as chemical resistance, solvent resistance, adhesion, and pencil hardness are improved, and the moisture absorption rate and moisture permeability can be reduced and the deep curability can also be improved.

[0118] In addition, (B) when the content of the photopolymerization initiator is within the above range, the undercut is not severe, the upper growth phenomenon (halation) is not large, so the resolution is excellent and a large number of solder resist openings can be formed. In addition, a high reflectivity can be maintained.

[0119] [(C) Weapon Filler]

[0120] A photosensitive resin composition according to one embodiment of the present invention can obtain high reflectance by including an inorganic filler.

[0121] Inorganic fillers include, for example, titanium oxide, zinc oxide, basic carbonate, basic sulfate, sulfate, zinc sulfide, antimony oxide, aluminum hydroxide, silica, barium sulfate, etc. For example, when a composition is implemented by mixing barium sulfate and silica and using them as an inorganic filler, the L value is 80 or more, the a value is -5 or more, and the b value is -5 or more. The L value may be measured by Hunter 1948. For example, when a composition is implemented by using a high content of titanium oxide and silica as inorganic fillers, the cured product of the composition has an L value of 90 or more, an a value of -3 or more, and a b value of -3 or more, thereby exhibiting high whiteness and reflectance. For example, when a composition is implemented by using at least one of titanium oxide and silica as an inorganic filler, the L value may be 95 or more, an a value of -2 or more, and a b value of -1 or more, thereby exhibiting the highest whiteness and reflectance.

[0122] For example, the manufacturing method of titanium oxide can be either the sulfuric acid method or the chlorine method, and for example, the chlorine method may be used. For example, sulfuric acid may not be used in the manufacturing process. Furthermore, the surface treatment of titanium oxide is not particularly limited, but may be titanium oxide treated with an acid other than sulfuric acid, such as hydrochloric acid, nitric acid, phosphoric acid, or acetic acid, during neutralization.

[0123] The titanium oxide may be of any structure, including rutile, anatase, and Ramsdelight types, and may be used alone or in combination of two or more types. Among these, Ramsdelight type titanium oxide is Ramsdelight type Li. 0.5 TiO2 can be obtained by performing chemical lithium oxide removal treatment.

[0124] Among the above, the use of rutile-type titanium oxide can further improve heat resistance, make it difficult for discoloration due to light irradiation to occur, and make it difficult for quality to deteriorate even in a strict usage environment. In particular, the heat resistance can be improved by using rutile-type titanium oxide surface-treated with aluminum oxide such as alumina. The content of rutile-type titanium oxide surface-treated with aluminum oxide in the total titanium oxide is, for example, 20 mass% or more, for example, 55 mass% or more, and the upper limit is 100 mass% or less, that is, the entire amount of titanium oxide may be rutile-type titanium oxide surface-treated with the above aluminum oxide. In addition, since anatase-type titanium oxide has a lower hardness than rutile-type titanium oxide, the formability of the composition is further improved when anatase-type titanium oxide is used. Rutile-type, anatase-type, and Ramsdilite-type titanium oxides, which are inorganic fillers, can also be used as white colorants.

[0125] In the photosensitive resin composition of the present invention, the blending amount of the (C) inorganic filler may be in the range of 20 to 70 mass%, for example, 25 to 70 mass%, based on the entire resin composition. The content of the (C) inorganic filler may be calculated based on solid content conversion. If the content of the (C) inorganic filler is within the above range, it is advantageous for high reflection, and if it is less than the above range, the reflectivity decreases, and if it exceeds the above range, cracks may occur.

[0126] In addition, rutile type chlorinated titanium dioxide T-550, T-580, R-630, R-820, CR-50, CR-60, R-90, CR-97 from Ishihara Sangyo Co., Ltd., Ti PURE R-706, R-902+, R931 from DuPont, TR-600, TR-700, TR-840 from Fuji Titanium Industry Co., Ltd., KR-270, KR-310, KR-380 from Titanium Industry Co., Ltd., CR-58, CR-90, R-630 from Ishihara Sangyo Co., Ltd., R-21 from Sakai-chem Co., Ltd., etc. can be used.

[0127] If the particle size of titanium oxide is too small, its fluidity may be poor, and conversely, if it is too large, its insertability into small diameter substrates may be poor. Considering these factors, the median particle size of the titanium oxide is in the range of 0.1 to 5 ㎛, for example, in the range of 0.1 to 1 ㎛, for example, in the range of 0.1 to 0.5 ㎛, and may be 0.36 ㎛. When the particle size of the titanium oxide is within the above range, it can exhibit high reflectivity. The above particle size was measured using a laser diffraction method.

[0128] In addition to titanium oxide, inorganic fillers such as silica such as barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, and spherical silica, talc, clay, Neuburg silica particles, boehmite, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, calcium zirconate, or metal powders such as copper, tin, zinc, nickel, silver, palladium, aluminum, iron, cobalt, gold, and platinum can be used. It is preferable that the inorganic filler be a spherical particle.

[0129] (C) Among inorganic fillers, barium sulfate includes precipitated barium sulfate #100, precipitated barium sulfate #300, precipitated barium sulfate SS-50, BARIACE B-30, BARIACE B-31, BARIACE B-32, BARIACE B-33, BARIACE B-34, BARIFINE BF-1, BARIFINE BF-10, BARIFINE BF-20, BARIFINE BF-40 (manufactured by Sakai Kagaku Kogyo Co., Ltd.), W-1, W-6, W-10, C300 (manufactured by Takehara Kagaku Kogyo Co., Ltd.).

[0130] (C) Among inorganic fillers, silica particles are not particularly limited and can be obtained by a method known to those skilled in the art. For example, they can be manufactured by burning silicon powder using the VMC (Vaporized Metal Combustion) method. The VMC method is a method in which a chemical flame is formed by a burner in an atmosphere containing oxygen, and a metal powder constituting a portion of the target oxide particle is injected into the chemical flame in an amount that forms a dust cloud, thereby causing knocking to obtain oxide particles. Examples of commercially available silica include the SO series manufactured by Admatex Co., Ltd. and the HPS series manufactured by Toagosei Co., Ltd. (HPS-0500, HPS-1000, HPS3500, etc.).

[0131] [Mercapto-modified (meth)acrylate]

[0132] The photosensitive resin composition according to one embodiment of the present invention can enhance surface hardening, improve gloss, and achieve high reflectivity by using a mercapto-modified (meth)acrylate.

[0133] In addition, when the mercapto-modified (meth)acrylate of the present invention is used in a photosensitive resin composition together with the above-described (C) inorganic filler, the surface curing of the photosensitive resin layer is improved, and the improvement in surface curing enables implementation of higher reflectivity and higher gloss.

[0134] The mercapto-modified (meth)acrylate of the present invention is a compound modified by introducing a mercapto group into an acrylate compound, wherein the acrylate compound may be a monofunctional or polyfunctional acrylate compound, and may be an aliphatic compound having 1 to 15 carbon atoms substituted with at least one functional group selected from the group consisting of an acryloyl group, an acryloyloxy group, and an acryloyloxyalkyl group, and examples thereof include pentane triacrylate.

[0135] The mercapto-modified (meth)acrylate of the present invention may be curable or may be active energy ray curable, and the mercapto-modified (meth)acrylate of the present invention can be obtained by Michael addition reaction of a polyfunctional thiol compound and a stoichiometrically excessive bifunctional or higher polyfunctional (meth)acrylate compound with a mercapto-modified (meth)acrylate. As polyfunctional thiol compounds, for example, polyisocyanates such as pentaerythritol tetrakis(3-mercaptopropionate) (molecular weight 489 g / mol), trimethylolpropane tris(3-mercaptopropionate) (molecular weight 399 g / mol), 1,3-bis(2-isocyanato-2-propyl)benzene tetrathiol (thiol) and polyfunctional thiol compounds such as trimethylolpropane tris(3-mercaptopropionate) are reaction products, polyisocyanates such as isophorone diisocyanate are reaction products, polyfunctional thiol compounds such as trimethylolpropane tris(3-mercaptopropionate) are reaction products, polyisocyanates such as hexamethylene diisocyanate are reaction products, polyfunctional thiols such as trimethylolpropane tris(3-mercaptopropionate) are reaction products. Polyfunctional thiol compounds of reaction products with compounds include 1,6-hexanedithiol (molecular weight 150 g / mol), ethylene glycol di-2-mercaptoacetate (molecular weight 210 g / mol), pentaerythritol tetrakis(2-mercaptoacetate) (molecular weight 433 g / mol), trimethylolpropane tris(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate) (molecular weight 238 g / mol), etc. For example, the mercapto-modified (meth)acrylate may contain two or more mercapto groups, or may contain three or more mercapto groups.

[0136] The above mercapto-modified (meth)acrylate may have a weight average molecular weight of 5,000 g / mol or less, 3,000 g / mol or less, or 2,000 g / mol or less. Since the weight average molecular weight is 5,000 g / mol or less, the mobility of the mercapto-modified (meth)acrylate molecules is reduced, so that the reduction in the reactivity of the active energy ray-curable coating film formation of the present invention can be suppressed. For example, if the reactivity is reduced, when the coating film is cured with UV-LED, the tackiness of the surface of the cured coating film increases, and the possibility of the problem of the coating film sticking to the printed matter when the printed matter is placed may increase.

[0137] In the photosensitive resin composition of the present invention, the content of the mercapto-modified (meth)acrylate may be 1 to 20 parts by weight, 1 to 10 parts by weight, or 1 to 7 parts by weight based on 100 parts by weight of the entire composition.

[0138] When the content of mercapto-modified (meth)acrylate is within the above range, surface hardening is enhanced, resulting in improved gloss, high reflectivity, less reduction in reflectivity after the manufacturing process, and superior crack resistance. Furthermore, gloss reduction due to reduced surface hardening can be suppressed, high reflectivity can be achieved, and the surface can be appropriately hardened to reduce brittleness of the coating and enhance resolution.

[0139] [Thermosetting acid value resin]

[0140] The photosensitive resin composition of the present invention includes (A) a carboxyl group-containing resin, but may additionally include a thermosetting acid resin in addition to the (A) resin.

[0141] The thermosetting acid value resin can exhibit excellent yellowing resistance when combined with the (A) resin. The photosensitive resin composition according to one embodiment of the present invention can exhibit excellent yellowing resistance by including the thermosetting acid value resin in a smaller amount than the (A) resin.

[0142] The thermosetting acid resin of the present invention may be, for example, a resin that exhibits electrical insulation properties by being cured by heating.

[0143] The thermosetting acid resin may include at least one selected from the group consisting of a benzene ring, a pyridine ring, a pyrimidine ring, and a triazine ring, and as the thermosetting acid resin of the present invention, for example, a melamine resin, a silicone resin, a resin having a styrene skeleton, etc. may be used, and for example, a resin having a styrene skeleton may be used.

[0144] In addition, the thermosetting acid value resin may contain a carboxyl group, and may be, for example, a carboxyl group-containing resin having a styrene skeleton. For example, the thermosetting acid value resin may be a mixture of a carboxyl group-containing resin having a styrene skeleton and a carboxyl group-containing resin other than a carboxyl group-containing resin having a styrene skeleton.

[0145] For example, if the thermosetting acid value resin is a carboxyl group-containing resin having a styrene skeleton, it may not have a photosensitive group such as an ethylenically unsaturated bond having a carboxyl group in the molecule, have a styrene skeleton in the molecule, have an average molecular weight of 10,000 to 50,000 g / mol, and have an acid value of 80 to 200 mgKOH / g. Such a carboxyl group-containing resin having a styrene skeleton can be synthesized by copolymerizing styrene as an essential monomer. By using a carboxyl group-containing resin having the properties in the above-described range, excellent touch-drying properties and flow-prevention effects of a cured film can be achieved.

[0146] Examples of carboxyl group-containing resins having a styrene skeleton include carboxyl group-containing resins (regardless of oligomers and polymers) that can be obtained by copolymerization with an unsaturated carboxylic acid such as (meth)acrylic acid and a compound containing an unsaturated group selected from styrene, α-methylstyrene, lower alkyl (meth)acrylate, isobutylene, etc. Here, lower alkyl can mean an alkyl group having 1 to 5 carbon atoms.

[0147] In the photosensitive resin composition of the present invention, the weight average molecular weight of the carboxyl group-containing resin having a styrene skeleton varies depending on the resin skeleton, but may be 10,000 g / mol to 50,000 g / mol, 10,000 g / mol to 25,000 g / mol, 10,000 g / mol to 20,000 g / mol, or 10,000 g / mol to 17,000 g / mol. By setting the weight average molecular weight to 10,000 g / mol or more, not only is the flow prevention effect improved, but also the tackiness is further improved, the moisture resistance of the exposed film is improved, and the film reduction during development can be suppressed and the deterioration of the resolution can be suppressed. In addition, by setting the weight average molecular weight to 50,000 g / mol or less, not only the flow prevention effect but also the developability and storage stability can be improved.

[0148] In the photosensitive resin composition of the present invention, the acid value of the carboxyl group-containing resin having a styrene skeleton may be 80 to 200 mgKOH / g, or 100 to 180 mgKOH / g. By setting the acid value of the carboxyl group-containing resin having a styrene skeleton to 80 mgKOH / g or more, the softening point may be increased, thereby improving tackiness and developability. On the other hand, by setting the acid value of the carboxyl group-containing resin having a styrene skeleton to 200 mgKOH / g or less, a suitable crosslinking density may be achieved so that stress is not generated during curing and a good coating film can be obtained.

[0149] In the photosensitive resin composition of the present invention, the carboxyl group-containing resin having a styrene skeleton has an aromatic ring because it has a styrene skeleton, and thus suppresses a decrease in reflectance and discoloration due to light irradiation and heat of the cured product, and can have excellent developability and touch-drying properties. The ratio of the styrene skeleton can be 10 to 80 mol%, 10 to 60 mol%, or 10 to 50 mol% based on the molecule. That is, when synthesizing the carboxyl group-containing resin having a styrene skeleton, 30 to 60 mol% of styrene can be used based on the total amount of monomers. When the ratio of the styrene skeleton of the carboxyl group-containing resin having a styrene skeleton is 10 mol% or more based on the molecule, compatibility with other components becomes good, and when it is 80 mol% or less based on the molecule, developability can become good.

[0150] A carboxyl group-containing resin having a styrene backbone can be manufactured by suspension polymerization to become a high molecular weight resin. As a result, a photosensitive resin composition using the resin can have an excellent tacky effect. Generally, when a carboxyl group-containing resin having a styrene backbone is manufactured by suspension polymerization, it becomes a high molecular weight resin. However, considering characteristics such as screen printing suitability, tackiness, and developability, the weight average molecular weight can be limited to the range of 10,000 to 50,000 g / mol. Therefore, in order to control the molecular weight, a chain transfer agent can be used when synthesizing a carboxyl group-containing resin having a styrene backbone.

[0151] In addition, a polymerization initiator can be used when synthesizing a carboxyl group-containing resin having a styrene backbone to promote polymerization. Examples of the polymerization initiator include BPO (benzoyl peroxide), t-butylperoxy-2-ethylhexanonate, AMBN (2,2'-azobis(2-methylbutyronitrile)), and the like, and for example, BPO (benzoyl peroxide) can be used. The blending amount of the polymerization initiator can be 0.1 to 10 wt%, or 0.1 to 6 wt%, in terms of solid content, based on 100 wt% of the carboxyl group-containing resin having a styrene backbone.

[0152] In the photosensitive resin composition of the present invention, the content of the thermosetting acid resin may be 0.1 to 15 wt%, 1 to 10 wt%, or 2 to 6 wt% based on the total weight of the composition. The photosensitive resin composition includes a solid content and a solvent.

[0153] If the content of the thermosetting acid resin is within the above range, the decrease in reflectivity and discoloration are suppressed, and the developability and touch-drying properties are excellent, so that the effect of improving reflectivity and the effect of preventing yellowing can be improved.

[0154] For example, thermosetting acid resins can be used in compositions for white solder resists.

[0155] [Silane coupling agent]

[0156] The photosensitive resin composition according to one embodiment of the present invention may further contain a silane coupling agent. By containing the silane coupling agent, the photosensitive resin composition can exhibit improved crack resistance, improved reflectivity, and superior gloss.

[0157] The silane coupling agent of the present invention may have an organic group such as a vinyl group, a styryl group, an acrylic group, a methacryl group, an isocyanurate group, an acid anhydride group, a ureide group, an epoxy group, an amino group, a methacryloxy group, a mercapto group, an isocyanate group, or an isocyanurate group.

[0158] Examples of silane coupling agents having a vinyl group include vinyltrimethoxysilane and vinyltriethoxysilane. Examples of silane coupling agents having a styryl group include p-styrylmethoxysilane. Examples of silane coupling agents having a methacryl group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. Examples of silane coupling agents having an acrylic group include 3-acryloxypropyltrimethoxysilane, etc. Silane coupling agents having an amino group include N-2-(aminoethyl)-3-aminopropyl methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxy-silyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyl trimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, etc. Silane coupling agents having a methacryloxy group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. Silane coupling agents having a mercapto group include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Examples of silane coupling agents having an isocyanate group include 3-isocyanate propyltriethoxysilane. Examples of silane coupling agents having an isocyanurate group include tris-(trimethoxysilylpropyl)isocyanurate. Examples of silane coupling agents having a ureide group include 3-ureidopropyltrialkoxysilane. Examples of silane coupling agents having an acid anhydride group include 3-(trimethoxysilyl)propylsuccinic anhydride.

[0159] The above silane coupling agent may be a silane coupling agent having an epoxy group, and may be, for example, 2-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, and the like, and may be, for example, 3-glycidoxypropyltriethoxysilane.

[0160] In the photosensitive resin composition of the present invention, the content of the silane coupling agent may be 0.1 to 5 wt%, 0.3 to 3 wt%, or 0.4 to 2 wt% relative to the entire composition. The composition includes a solid content and a solvent.

[0161] When the content of the silane coupling agent is within the above range, the composition may have excellent crack resistance, high reflectivity, excellent adhesion, and low tackiness, making it suitable for film formation.

[0162] The silane coupling agent may be a commercially available product, and examples thereof include KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402 and KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103P, KBM-573, KBM-575, KBM-9659, KBM-585A, KBM-802, KBM-803, KBE-9007N, X-12-967C manufactured by Shin-Etsu Chemical Co., Ltd.

[0163] For example, a silane coupling agent can be used in a composition for a white solder resist.

[0164] [Resin with urethane bonds]

[0165] The photosensitive resin composition according to one embodiment of the present invention may further contain a resin having a urethane bond. The resin having a urethane bond may be a resin with excellent flexibility.

[0166] The photosensitive resin composition uses a resin having a urethane bond, so it can be laminated to a uniform thickness without breaking even on a flexible substrate or a thin sheet, and has excellent resistance to cracking or breaking when subjected to external impact or when bent.

[0167] The resin having a urethane bond of the present invention may include a modified urethane resin, and the resin having a urethane bond may be an ester type urethane, an ether type urethane, a modified urethane acrylate, a modified urethane epoxy, a silicone modified urethane, a fluorine-based modified urethane, etc., and may be, for example, a modified urethane epoxy acrylate containing an epoxy group.

[0168] As the resin having a urethane bond of the present invention, a known compound having a urethane bond can be used. For example, a reaction product of an isocyanate compound (e.g., monoisocyanate, diisocyanate, polyisocyanate) and a compound having an OH group (e.g., a polyhydric alcohol such as a monohydric alcohol, polyester polyol, polyether polyol, or epoxy (meth)acrylate), or a modified product thereof, may be mentioned.

[0169] The resin having a urethane bond of the present invention may be one having a carboxyl group or an epoxy group, or one having a (meth)acryloyl group, and examples thereof include the following carboxyl group-containing resin (1), epoxy group-containing resin (2), (meth)acryloyl group-containing resin (3), (4), (5), etc.

[0170] (1) A carboxyl group-containing photosensitive polyurethane resin obtained by a polyaddition reaction between a reaction product of a diisocyanate and a monocarboxylic acid compound having an ethylenically unsaturated double bond, such as a bifunctional epoxy resin (meth)acrylate, such as a biisocyanate and a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bixilenol epoxy resin, a phenol type epoxy resin, a partial anhydride thereof, or a modified product thereof, and a carboxyl group-containing dialcohol compound and a diol compound.

[0171] (2) A urethane-modified epoxy resin having a urethane bond and two or more epoxies in the molecule obtained by reacting a urethane bond-containing compound having an isocyanate group obtained by reacting a polyhydroxy compound and a polyisocyanate compound with an epoxy compound containing a hydroxy group.

[0172] (3) A urethane resin obtained by polyaddition reaction of a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, an aromatic diisocyanate, and a diol compound such as a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, an epoxy resin having a hydroxyl group (when this is used, a urethane resin having an epoxy group can be obtained), a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

[0173] (4) A photosensitive polyurethane resin obtained by replacing part or all of the diisocyanate in the above (3) with a reaction product of isophorone diisocyanate and pentaerythritol triacrylate, and / or a compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule, and by a polyaddition reaction of such isocyanate and the diol compound.

[0174] (5) A terminal (meth)acrylated photosensitive polyurethane resin in which a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as hydroxyalkyl (meth)acrylate, is added during the synthesis of one of the resins (3) and (4) above.

[0175] Additionally, as described above, one resin may have at least two types of carboxyl groups, epoxy groups, or methacryloyl groups.

[0176] The resin having the above urethane bond may be (1) among carboxyl group-containing resins, (2) among epoxy group-containing resins, and (5) among (meth)acryloyl group-containing resins.

[0177] The diisocyanate can be, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate, or an alicyclic polyisocyanate. The aromatic polyisocyanates can be, for example, 4,4'-diphenylmethane diisocyanate, 2,4-diisocyanate-2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate-o-xylene diisocyanate, m-xylene diisocyanate, and 2,4-trilene dimer. The aliphatic polyisocyanates can be, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate), and isophorone diisocyanate. The alicyclic polyisocyanate may be, for example, bicycloheptanetriisocyanate. The diisocyanate may be, for example, an aliphatic isocyanate.

[0178] When the resin having a urethane bond is a carboxyl group-containing resin having a urethane bond, the acid value of the carboxyl group-containing resin can be 40 to 200 mgKOH / g, or 45 to 120 mgKOH / g. When the acid value of the carboxyl group-containing resin is in the range of 40 to 200 mgKOH / g, the adhesion of the cured film is obtained, and alkali development becomes easy, so dissolution of the exposed area by the developer is suppressed, so that the line does not become narrower than necessary, and a normal resist pattern can be easily drawn.

[0179] When the resin having a urethane bond is a carboxyl group-containing resin having a urethane bond, the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but may be 2,000 to 150,000 g / mol, 5,000 to 50,000 g / mol, or 2,000 to 50,000 g / mol. When the weight average molecular weight is within the above range, the tackiness is good, the moisture resistance of the cured film is good, and the occurrence of film shrinkage during development can be reduced. In addition, when the weight average molecular weight is within the above range, the resolution and developability are good, and the storage stability can be improved.

[0180] Examples of commercially available resins having urethane bonds (e.g., carboxyl group-containing resins having urethane bonds) include UXE-3000, UXE-3002, UXE-3024, UXE-3086, UXE-3044, UXE-3061, UXE-3063, UXE-3064, UXE-3065, UXE-3067 (Nippon Gunyaku Co., Ltd.), EPU-7N (urethane-modified epoxy resin; ADEKA Co., Ltd.), Ebecryl 210 (aromatic urethane acrylate; Daicel Allnex Co., Ltd.).

[0181] In the photosensitive resin composition of the present invention, the content of the resin having a urethane bond may be 0.1 to 15 wt%, 5 to 13 wt%, or 8 to 12 wt%, based on the total composition. The composition includes a solid content and a solvent. When the content of the resin having a urethane bond is within the above range, the composition has excellent flexibility and crack resistance, and can exhibit appropriate tackiness, excellent printability, and excellent drying properties.

[0182] In the photosensitive resin composition of the present invention, the weight average molecular weight of the resin having a urethane bond may be 2,000 to 150,000 g / mol, or may be 2,000 to 50,000 g / mol. When the weight average molecular weight of the resin having a urethane bond is within the above range, excellent crack resistance and flexibility can be achieved.

[0183] For example, a resin having a urethane bond can be used in a composition for a white solder resist.

[0184] [Other optional ingredients]

[0185] The photosensitive resin composition of the present invention may optionally contain various additives, as needed. Specifically, a thermosetting catalyst, a dispersant, an antioxidant, a colorant, an epoxy resin, an oxetane compound, a (meth)acrylic resin, various other additives, or a mixture of two or more thereof may be added. The optional components may contain one or more of the following materials.

[0186] Epoxy resin

[0187] The epoxy resin of the present invention may be a known, commonly used compound having one or more epoxy groups. For example, the epoxy resin may be one that does not overlap with the components (A) to (G) described above. For example, it may be a compound having two or more epoxy groups. For example, it may be a compound having two or more epoxy groups in one molecule, such as a monoepoxy compound such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl (meth)acrylate, bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic ring epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4'-diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, tris(2,3-epoxypropyl)isocyanurate, triglycidyltris(2-hydroxyethyl)isocyanurate. These can be used alone or in combination of two or more types to suit the required characteristics.

[0188] Examples of compounds having two or more epoxy groups include jER828, jER834, jER1001, jER1004 of Mitsubishi Chemical Co., Ltd., Epiclone 840, Epiclone 850, Epiclone 1050, Epiclone 2055 of DIC Co., Ltd., Epototo D-011, YD-013, YD127, YD-128 of Nittesu Chemical & Materials, DER317, DER331, DER661, DER664 of Dow Chemical Japan Co., Ltd., Sumiepoxy ESA-011, ESA-014, ELA-115, ELA128 of Sumitomo Chemical Co., Ltd., AER330, AER331, AER661, AER664 of Asahi Kasei Materials Co., Ltd. (all Bisphenol A type epoxy resin (trade name); jERYL903 of Mitsubishi Chemical Co., Ltd., Epichron 152, Epichron 165 of DIC Co., Ltd., Epototo YDE-400, YDE-500 of Nittesu Chemical & Materials Co., Ltd., DER542 of Dow Chemical Japan Co., Ltd., Sumiepokishi ESB-400, ESB-700 of Sumitomo Chemical Co., Ltd., AER711, AER714 of Asahi Kasei Materials Co., Ltd., etc. (all trade names); Mitsubishi Chemical Corporation's jER152, jER154, Dow Chemical Japan Co., Ltd.'s DEN431, DEN438, DIC Corporation's Epichron N-730, Epichron N-770, Epichron N-865, Nippon Chemical & Materials Co., Ltd.'s Epototo YDC-701, YDC-704, Nippon Chemical Co., Ltd.'s EPPN-201, EPPN-1025, EPPN-1020, EPPN-104S, RE-306, NC-3000, Sumitomo Chemical Co., Ltd.'s Sumiepoxy ESCN-195X, ESCN-220, Asahi Kasei Materials Co., Ltd.Noflak type epoxy resins such as ECN-235, ECN-299, YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704, YDCN-704A of Nittesu Chemical & Materials Co., Ltd., and Epichron N-680, N-690, N-695 of DIC Co., Ltd. (all trade names); Bisphenol F type epoxy resins such as Epichron 830 of DIC Co., Ltd., jER807 of Mitsubishi Chemical Co., Ltd., and Epitoto YDF-175, YDF-2004 of Nittesu Chemical & Materials Co., Ltd. (all trade names); Hydrogenated bisphenol A type epoxy resins such as Epototo ST-2004, ST-2007, and ST-3000 (trade names) of Nittesu Chemical & Materials Co., Ltd.; Glycidylamine type epoxy resins such as JER 604 of Mitsubishi Chemical Co., Ltd., Epototo YH-434 of Nittesu Chemical & Materials Co., Ltd., and Sumi Epoxy ELM-120 of Sumitomo Chemical Co., Ltd. (all trade names); Hydantoin type epoxy resins; Alicyclic epoxy resins such as Celoxide 2021 of Daicel Co., Ltd. (all trade names); YL-933 of Mitsubishi Chemical Co., Ltd., and TEN of Dow Chemical Japan Co., Ltd., EPPN-501, EPPN-502, etc. (all trade names); Bixilenol type or biphenol type epoxy resins or mixtures thereof, such as YL-6056, YX-4000, YL-6121 (all trade names) of Mitsubishi Chemical Co., Ltd.; Bisphenol S type epoxy resins, such as EBPS-200 of Nippon Kayaku Co., Ltd., EPX-30 of ADEKA Co., Ltd., EXA-1514 (trade names) of DIC Co., Ltd.; Bisphenol A novolac type epoxy resins, such as jER 157S (trade name) of Mitsubishi Chemical Co., Ltd.; Tetraphenylolethane type epoxy resins, such as jER YL-931 of Mitsubishi Chemical Co., Ltd. (all trade names); Heterocyclic epoxy resins, such as TEPIC of Nissan Chemical Industries, Ltd. (all trade names); Diglycidyl phthalate resins such as Brenmer DGT of Nichiyu Co., Ltd.; tetraglycyrrhizyl xylenol ethane resins such as ZX-1063 of Nittetsu Chemical & Materials Co., Ltd.; naphthalene group-containing epoxy resins such as ESN-190 and ESN-360 of Nittetsu Chemical & Materials Co., Ltd., and HP-4032, EXA-4750, and EXA-4700 of DIC Co., Ltd.; epoxy resins having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H of DIC Co., Ltd.; glycidyl methacrylate copolymerization epoxy resins such as CP-50S and CP-50M of Nichiyu Co., Ltd.; and copolymerization epoxy resins of cyclohexylmaleimide and glycidyl methacrylate. Examples include, but are not limited to, CTBN-modified epoxy resins (e.g., YR-102 and YR-450 from Nittsu Chemical & Materials Co., Ltd.). Among these, for example, bisphenol A-type epoxy resins, heterocyclic epoxy resins, or mixtures thereof may be used, as they have superior discoloration resistance. These epoxy resins may be used singly, or two or more may be used in combination.

[0189] In the photosensitive resin composition of the present invention, the epoxy resin may be a bisphenol-based epoxy resin, and for example, may be an epoxy resin having two or more epoxy groups in the bisphenol-based epoxy series. The blending amount of the bisphenol-based epoxy resin having two or more epoxy groups used in the present invention may be 1 to 15 wt%, may be in the range of 1 to 12 wt%, or may be in the range of 3 to 12 wt%, based on the total composition. The composition includes a solid content and a solvent.

[0190] When the content of the epoxy resin is within the above range, the coating film formed by the composition has excellent adhesion, heat resistance, and pencil hardness, is well cured, and can solve the problems of yellowing and difficulty in implementing high reflectivity after processing.

[0191] In the photosensitive resin composition of the present invention, the weight average molecular weight of the epoxy resin may be 150 to 100,000 g / mol.

[0192] Oxetane compound

[0193] Next, we will explain oxetane compounds. General formula (I) below:

[0194]

[0195] (In the formula R 1Specific examples of oxetane compounds containing an oxetane ring represented by (wherein represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) include 3-ethyl-3-hydroxymethyloxetane (Dong-A Synthetic Co., Ltd., trade name OXT-101), 3-ethyl-3-(phenoxymethyl)oxetane (Dong-A Synthetic Co., Ltd., trade name OXT-211), 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (Dong-A Synthetic Co., Ltd., trade name OXT-212), 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene (Dong-A Synthetic Co., Ltd., trade name OXT-121), bis(3-ethyl-3-oxetanylmethyl)ether (Dong-A Synthetic Co., Ltd., trade name OXT-221), etc. In addition, phenol novolak type oxetane compounds, etc. are also included. These oxetane compounds may be used in combination with the above epoxy compounds or may be used alone.

[0196] <(Meta)Acrylic Resin>

[0197] (Meth)acrylic resin is a photocurable resin. The photocurable resin is not particularly limited as long as it is a resin that exhibits electrical insulation properties by being cured by irradiation with active energy rays. For example, it may be a compound having one or more ethylenically unsaturated bonds in its molecule. For example, the (meth)acrylic resin may not overlap with the components (A) to (G) described above.

[0198] The compound having the above-mentioned ethylenically unsaturated bond may be a known photopolymerizable oligomer, photopolymerizable monomer, photopolymerizable vinyl monomer, etc. The photopolymerizable oligomer may be an unsaturated polyester oligomer, a (meth)acrylate oligomer, etc. The (meth)acrylate oligomer may be an epoxy (meth)acrylate such as phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, bisphenol type epoxy (meth)acrylate, urethane (meth)acrylate, epoxy urethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polybutadiene modified (meth)acrylate, etc.

[0199] Photopolymerizable monomers or photopolymerizable vinyl monomers include those known in the art, for example, styrene derivatives such as styrene, chlorostyrene, and α-methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate, and vinyl benzoate; ethers such as vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinylcyclohexyl ether, ethylene glycol monobutyl ether, and triethylene glycol monomethyl ether; (meth)acrylamides such as acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethyl acrylamide, and N-butoxymethylacrylamide; Aryl compounds such as triallyl isocyanurate, diaryl phthalate, and diaryl isophthalate; (meth)acrylic acid esters such as 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, and phenoxyethyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and pentaerythritol tri(meth)acrylate; alkoxyalkylene glycol mono(meth)acrylates such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; Alkylene polyol poly(meth)acrylates such as ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; polyoxyalkylene glycol poly(meth)acrylates such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane tri(meth)acrylate; poly(meth)acrylates such as hydroxypivalic acid neopentyl glycol ester di(meth)acrylate;Examples include isonalate-type poly(meth)acrylates such as tris[(meth)acryloxyethyl]isocyanurate, and these can be used alone or in combination of two or more.;

[0200] In the photosensitive resin composition of the present invention, the (meth)acrylic resin may be an unsaturated polyester oligomer, a (meth)acrylate oligomer, or the like, and may be, for example, a 6-functional flexible acrylic oligomer. The blending amount of the (meth)acrylic resin may be 1 to 15 wt%, 1 to 10 wt%, or 5 to 10 wt% based on the total composition. The composition includes a solid content and a solvent. When the content of the (meth)acrylic resin is within the above range, the resolution and undercut are excellent, and the coating film can be cured to an appropriate level.

[0201] <Thermocuring catalyst>

[0202] In the composition of the present invention, at least one curing agent or curing catalyst may be further added as a thermosetting catalyst. For example, the thermosetting catalyst may not overlap with the aforementioned components.

[0203] The curing agent can be, for example, a polyfunctional phenol compound, a polycarboxylic acid and anhydride thereof, an aliphatic or aromatic primary or secondary amine, a polyamide resin, an isocyanate compound, a polymercapto compound, etc. The curing agent can be, for example, a polyfunctional phenol compound, a polycarboxylic acid and anhydride thereof, and excellent workability and insulation can be obtained by using such a curing agent. The polyfunctional phenol compound is not particularly limited as long as it is a compound having two or more phenolic hydroxyl groups in one molecule, and can be, for example, a known or commonly used one. For example, the polyfunctional phenol compound can be a phenol novolac resin, a cresol novolac resin, bisphenol A, allylated bisphenol A, bisphenol F, a novolac resin of bisphenol A, or a vinylphenol copolymer resin. The polyfunctional phenol compound can be, for example, bisphenol A, thereby providing high reactivity and enhancing heat resistance. A polyfunctional phenol compound can undergo an addition reaction with at least one of an epoxy compound or an oxytane compound in the presence of a suitable curing catalyst. The polycarboxylic acid and its acid anhydride can be, for example, a compound having two or more carboxyl groups in one molecule and its acid anhydride, and can be, for example, a copolymer of (meth)acrylic acid, a copolymer of maleic anhydride, a condensate of a dibasic acid, etc. Commercially available products include Joncryl (product group name) from BASF, SMA Resin (product group name) from Satoma, and polyazelaic anhydride from Shin Nippon Rika.

[0204] In addition, the curing catalyst may be a compound that can act as a curing catalyst in the reaction between a thermosetting resin such as an epoxy compound or an oxetane compound and a curing agent, or a compound that acts as a polymerization catalyst when a curing agent is not used. Specifically, the curing catalyst may be, for example, a tertiary amine, a tertiary amine salt, a quaternary ammonium salt, a tertiary phosphine, a crown ether compound, or a phosphonium ylide, and any of these may be used singly or in combination of two or more.

[0205] For example, imidazoles such as 2E4MZ, C11Z, C17Z, 2PZ with the trade names, imidazole AZINE compounds such as 2MZ-A, 2E4MZ-A with the trade names, isocyanurates of imidazoles such as 2MZ-OK, 2PZ-OK with the trade names, imidazole hydroxymethyl compounds such as 2PHZ, 2P4MHZ with the trade names (trade name; Shikoku Kasei Industry Co., Ltd.), dicyandiamide and its derivatives, melamine and its derivatives, diaminomaleonitrile and its derivatives, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, bis(hexamethylene)triamine, triethanolamine, diaminodiphenylmethane with the trade names, 1,8-diazabicyclo[5,4,0]undecene-7 (trade name DBU, San-Apro Co., Ltd.), It may be an organic phosphine compound such as 3.9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane (trade name ATU, Ajinomoto Co., Ltd.) or triphenylphosphine, tricyclohexylphosphine, tributylphosphine, or methyldiphenylphosphine.

[0206] In the photosensitive resin composition of the present invention, the curing catalyst may be an amine-based, phosphine-based, or imidazole-based curing catalyst, and for example, may be a melamine-based amine curing catalyst. The blending amount of the curing catalyst may be 0.1 to 15 wt%, 0.1 to 10 wt%, or 0.1 to 3 wt% relative to the entire composition.

[0207] When the content of the above curing catalyst is within the above range, the coating film is sufficiently cured, so that the adhesion, pencil hardness, and heat resistance are excellent, and the curing time is appropriately maintained, and the deterioration of the developability can be prevented.

[0208] Antioxidant

[0209] The photosensitive resin composition of the present invention may also contain an antioxidant. By containing an antioxidant, not only can the effect of suppressing discoloration by preventing oxidative deterioration of the curable resin, etc. be obtained, but also the effect of improving heat resistance and improving resolution (line width reproducibility) can be obtained. In other words, depending on the type of white colorant, there are cases where resolution is deteriorated by reflecting and absorbing light, but by containing an antioxidant, good resolution can be obtained regardless of the type of white colorant. The antioxidant may be a radical scavenger that neutralizes generated radicals, or a peroxide decomposition inhibitor that decomposes generated peroxides into harmless substances and prevents the generation of new radicals, and may be used alone or in combination of two or more.

[0210] Antioxidants that act as radical scavengers include, for example, phenolic compounds such as hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2-methylene-bis(4-methyl-6-t-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3',5'-di-t-butyl-4-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, and quinone compounds such as menaquinone and benzoquinone. It can be an amine compound such as a compound, bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate, phenothiazine, etc. As a commercially available product, for example, IRGANOX1010 (product name of BASF Japan Co., Ltd.) can be used.

[0211] In addition, antioxidants that act as peroxide decomposers include, for example, phosphorus compounds such as triphenyl phosphite, sulfur compounds such as pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, and distearyl-3,3'-thiodipropionate.

[0212] For example, the antioxidant may be a phenolic compound, and its use can produce an anti-discoloration effect, improved heat resistance, and better resolution.

[0213] Additionally, antioxidants, such as phenolic antioxidants, can be used in combination with heat stabilizers. When used in combination, they can exhibit even better effects.

[0214] The heat-resistant stabilizer may be, for example, a phosphorus-based, hydroxylamine-based, or sulfur-based heat-resistant stabilizer. The heat-resistant stabilizer may be used alone or in combination of two or more types.

[0215] For example, the antioxidant may be a hydroxylamine-based antioxidant, a sulfur-based antioxidant, or a phenol-based antioxidant. When a phenol-based antioxidant is used, the blending amount may be 0.01 to 5 wt%, or 0.03 to 3 wt%, based on the total composition. By setting the blending amount of the antioxidant to 0.01 to 1 wt% or more, the effect of adding the antioxidant can be reliably obtained, and when it is 1 wt% or less, a good alkaline development can be obtained without inhibiting the photoreaction, and the touch-drying property and the coating film properties can also be well secured.

[0216] Organic solvents

[0217] The photosensitive resin composition of the present invention may contain an organic solvent for purposes such as preparing the composition or adjusting viscosity when applying it to a substrate or base material. Examples of the organic solvent include known and commonly used organic solvents such as esters; aliphatic hydrocarbons such as octane and decane; and petroleum solvents such as petroleum ether, petroleum naphtha, and solvent naphtha. These organic solvents may be used alone or in combination of two or more.

[0218] Colorant

[0219] The photosensitive resin composition of the present invention may contain a colorant.

[0220] The colorant may include one or more types of blue colorant, green colorant, yellow colorant, white colorant, black colorant, and red colorant in appropriate combination. Any of pigments, dyes, and pigments is possible. In the present invention, the pigment refers to a compound classified as a pigment in the Color Index (CI; published by the Society of Dyes and Colorists), and the dye refers to a compound classified as other than a solvent or Lumogen (registered trademark), etc. However, from the viewpoint of reducing environmental impact and the effect on the human body, it is preferable that the colorant be one that does not contain halogen.

[0221] (1) Blue colorants include metal-substituted or unsubstituted phthalocyanine compounds and anthraquinone compounds, and pigments include compounds classified as pigments, specifically, those with the following color index numbers: Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60. As for dyes, solvent blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70, etc. can be used.

[0222] (2) As green colorants, there are metal-substituted or unsubstituted phthalocyanine-based, anthraquinone-based, and perylene-based pigments, and specifically, pigment green 7, pigment green 36, solvent green 3, solvent green 20, and solvent green 28 can be used.

[0223] (3) Yellow coloring agents include anthraquinones, isoindolinones, condensed azos, benzimidazolone, monoazo, and disazo, and the following are specific examples. (Anthraquinone type) Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202; (Isoindolinone type) Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185; (Condensed azo type) Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180; (Benzimidazolone) Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181; (Monoazo) Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1, 65, 73, 74, 75, 97, 100, 104, 105, 111,116, 167, 168, 169, 182, 183; (Disazo) Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

[0224] (4) Examples of black coloring agents include titanium black, carbon black, graphite, iron oxide, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, aniline pigments, molybdenum sulfide, and bismuth sulfide.

[0225] (5) Examples of red colorants include monoazo, disazo, monoazo lake, benzimidazolone, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone, and the following are specific examples.

[0226] (Monoazo) Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151,170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269; (Disazo) Pigment Red 37, 38, 41; (Monoazo lake type) Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1, 68; (Benzimidazolone type) Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208; (Diketopyrrolopyrrole type) Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272; (Condensed azo) Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242; (Anthraquinone) Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207; (Quinacridone) Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

[0227] In this case, the mixing amount of the colorant may be in the range of 0.01% to 7% by mass for each of the blue, green, yellow, black, and red colorants, for example, 0.5% to 6% by mass, or 1% to 5% by mass, based on 100 parts by mass of the total amount of the composition.

[0228] Dispersant

[0229] A dispersant may be added to improve the storage stability, coatability, printability, and cohesion of the photosensitive resin composition. The dispersant is not particularly restricted, and known ones can also be used. Examples of the dispersant include phosphate esters or acrylic copolymers having acidic or basic groups or both, polyamines, polyurethanes, polyesters, polyacrylates, and their phosphates, alkyl ammonium salt aliphatic carboxylates, higher alcohol sulfuric esters, alkyl sulfonic acids, polyethers, polyester carboxylic acids, copolymers containing acid groups, pigment-affinity block copolymers, phosphate ester compounds, polyether phosphate ester compounds, fatty acid ester compounds, alkylene oxide copolymers, modified polyether polymers, and fatty acid derivatives. By including a dispersant, the viscosity of the photosensitive resin composition is reduced, and the dispersion of solid particles of the composition is improved, thereby preventing aggregation, thereby improving coatability and processability. Specifically, examples thereof include, but are not limited to, EVONIK (registered trademark, manufactured by Evonik), DISPERBYK (registered trademark) series (manufactured by BYK), EFKA (registered trademark) series (manufactured by BASF), SOLSPERSE (registered trademark) series (manufactured by Nippon Lubrizol), Disparlon series (manufactured by Kusumoto Kasei), and Flowlen series (manufactured by Kyoei Chemicals). The dispersant may be used singly by one type, or two or more types may be used in combination. The content of the dispersant may be 0.5 mass% to 9 mass% with respect to the total amount of the composition, for example, 1 mass% to 7 mass%, or 1 mass% to 5 mass%.

[0230] Other additives

[0231] In addition, the photosensitive resin composition of the present invention may contain other commonly known additives in the field of electronic materials. Examples of the other additives include thermal polymerization inhibitors, ultraviolet absorbers, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial and antifungal agents, antifoaming agents, leveling agents, thickeners, adhesion-imparting agents, thixotropic agents, photoinitiation aids, sensitizers, curing accelerators, release agents, surface treatment agents, dispersants, dispersing aids, surface modifiers, stabilizers, and the like.

[0232] [Dry film and its manufacturing method]

[0233] Another embodiment of the present invention relates to a dry film having a photosensitive resin layer formed by applying and drying a photosensitive resin composition on a first film.

[0234] When forming a dry film, first, the composition of the present invention is diluted with an organic solvent to adjust the viscosity to an appropriate level, and then applied to a first film with a uniform thickness, for example, in the range of 40 to 60 μm, using a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, micro gravure coater, spray coater, or the like. Thereafter, the applied composition is dried at a temperature typically in the range of 40 to 120°C for 1 to 30 minutes to form a photosensitive resin layer, thereby forming a dry film.

[0235] There is no particular limitation on the thickness of the coating film, but generally, the thickness after drying may be 10 to 150 ㎛, 10 to 80 ㎛, or 10 to 60 ㎛.

[0236] As the first film, a plastic film is used, and for example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamide-imide film, a polypropylene film, a polystyrene film, etc. can be used, and for example, it can be polyethylene terephthalate. There is no particular limitation on the thickness of the first film, but it can generally be appropriately selected within the range of 10 to 150 ㎛. In addition, it can be applied to a metal foil such as a copper foil or an aluminum foil. In addition, the first film used can be subjected to a peeling treatment such as acrylic or silicone.

[0237] When the dry film of the present invention is white, it can be used to reflect light generated from light-emitting diodes (LEDs) or electroluminescent (EL) used as light sources in backlights of liquid crystal displays, such as lighting devices, mobile terminals, notebook computers, tablet PCs, monitors, smartphones, personal computers, automobile displays, headlamps, and televisions. The dry film of the present invention can be applied to LEDs and light-emitting PCBs, etc.

[0238] In addition, the colored (blue, green, black) dry film of the present invention can be applied to PCBs or component substrates of electronic devices such as electronic watches, automobiles, medical device substrates, credit card substrates, electronic wristwatches, earphones, smartphones, cameras, camera modules, and micro LED displays.

[0239] To create a cured film on a printed wiring board using a dry film, a second film, intended for the purpose of protecting the dry film, is peeled off, the exposed resin layer of the dry film is superimposed on the circuit-formed substrate and attached using a laminator or the like, thereby forming a resin layer on the circuit-formed substrate. Subsequently, the formed resin layer is exposed, developed, heated, and then cured to form a cured film. The second film can be peeled off at any stage, either before or after exposure.

[0240] [Curing agent and its manufacturing method]

[0241] The cured product of the present invention can be formed by curing the photosensitive resin composition of the present invention or the solder resist layer of the dry film of the present invention.

[0242] The cured product of the present invention can be suitably used for printed wiring boards and electronic components, etc. The cured product of the present invention can have a high photoreactivity, low moisture absorption and moisture permeability, low ion migration, low outgassing content, and excellent pencil hardness and HAST resistance.

[0243] For example, the cured product of the present invention may be a white or colored (blue, green, black) solder resist.

[0244] The above solder resist can be manufactured by forming a pattern by applying the photosensitive resin composition of the present invention on a substrate to form a photosensitive resin layer, selectively exposing the photosensitive resin layer to an active energy ray through a photomask having a predetermined pattern formed thereon, and developing the unexposed portion with a dilute alkaline aqueous solution (e.g., 0.3 to 3 wt% sodium carbonate aqueous solution). Alternatively, in the case of a dry film, after exposure, the first film of the dry film is peeled off and then developed, thereby forming a patterned solder resist on the substrate. Additionally, as long as the properties are not impaired, the first film may be peeled off from the dry film before exposure, and the exposed resin layer may be exposed and developed.

[0245] [Printed wiring board and manufacturing method thereof]

[0246] The printed wiring board of the present invention may include a cured film formed by curing a cured product of the photosensitive resin composition of the present invention or a photosensitive resin layer of the dry film of the present invention.

[0247] The printed wiring board of the present invention may include a cured product obtained from the photosensitive resin composition of the present invention or the photosensitive resin layer of the dry film. The method for manufacturing the printed wiring board of the present invention includes, for example, adjusting the viscosity of the photosensitive resin composition of the present invention to a viscosity suitable for the coating method using the organic solvent, coating the composition on a substrate by a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, a curtain coating method, or the like, and then drying (temporarily drying) the organic solvent included in the composition at a temperature of 60 to 100°C to volatilize it, thereby forming a tacky-free resin layer. In addition, in the case of a dry film, the resin layer may be bonded to the substrate by a laminator or the like so that it comes into contact with the substrate, and then the first film may be removed to form a resin layer on the substrate.

[0248] The above-mentioned substrates include not only printed wiring boards and flexible printed wiring boards formed with copper or the like, but also copper-clad laminates for high-frequency circuits using materials such as paper phenol, paper epoxy, glass fiber epoxy, glass polyimide, glass fiber / epoxy, glass fiber / paper epoxy, synthetic fiber epoxy, fluororesin, polyethylene, polyphenylene ether, and polyphenylene oxide cyanate, and examples thereof include FR-4 substrates, copper-clad laminates of all grades (FR-4, etc.), other metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, and wafer substrates.

[0249] A method of laminating a dry film on a substrate can be performed by applying pressure and heating using a vacuum laminator or the like. By using such a vacuum laminator, even if the circuit board surface is uneven when a circuit-formed substrate is used, the dry film adheres closely to the circuit board, preventing the inclusion of air bubbles and improving the relief of undulating areas on the substrate surface. The pressure conditions can be approximately 0.1 to 2.0 MPa, and the temperature conditions can be 40 to 120°C.

[0250] In addition, a cured film having excellent properties such as adhesion and hardness can be formed by i) irradiating the cured product with an active energy ray and then heat-curing (e.g., 100 to 220°C), ii) irradiating the cured product with an active energy ray after heat-curing, iii) only irradiating the cured product with an active energy ray, or iv) final curing only by heat-curing.

[0251] The cured product of the present invention can form a cured film having excellent properties such as high reflectivity, excellent yellowing resistance, and excellent crack resistance by curing it by heating it at a temperature of, for example, 100 to 220°C.

[0252] The exposure device used for the above active energy ray irradiation may be a device equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc., and may irradiate ultraviolet (UV) rays in the range of 350 to 450 nm, and may also be a direct drawing device (e.g., a laser direct imaging device that directly draws CAD data on a computer with a laser). The maximum wavelength of the direct drawing device lamp light source or laser light source may be in the range of 350 to 450 nm. The exposure for image formation varies depending on the thickness, etc., but is generally 10 to 1,000 mJ / cm. 2 It can be 20~800mJ / cm 2 It could be.

[0253] The above-mentioned developing method may be a dipping method, a shower method, a spray method, a brush method, etc., and an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, or amines may be used as the developing solution.

[0254] The printed wiring board of the present invention may include a dry film including one or more layers formed from the photosensitive resin composition.

[0255] When forming a printed wiring board, a dry film can be placed on a test substrate and vacuum lamination can be performed to transfer the dry film onto the test substrate.

[0256] After that, the first film is peeled off, and the substrate to which the dry film from which the first film is peeled is transferred can be exposed to UV light using an exposure device. When exposed in this way, the exposed portion (the portion irradiated with light) can be cured. After exposure, the substrate is cooled to room temperature and then placed in a developer to develop the unexposed portion with an alkaline aqueous solution, so that the resist pattern formation can be completed. The substrate on which the pattern has been formed through development can be final cured (post-cured) in an oven at 150°C for 1 hour, thereby completing the substrate manufacturing. After the final curing, a reflow process is performed, and then a chip mounting process is performed.

[0257] The method for manufacturing a printed wiring board including the cured product of the present invention can peel off the first film after, for example, performing an exposure operation after a lamination process.

[0258] <Example>

[0259] Hereinafter, the present invention will be described in detail using examples. The present invention is not limited to the following examples.

[0260] Preparation of photosensitive resin composition

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267] Preparation of dry film of photosensitive resin composition

[0268] In a dust-free room, a comma coater was used to coat (1) a first film (PET film) (XD-500P manufactured by Toray Industries, Inc., film thickness: 25 μm) with a uniform thickness (60 μm) of the compositions of each example and comparative example. (2) The coated compositions were dried in four temperature chambers (Chamber 1: 60 °C, Chamber 2: 80 °C, Chamber 3: 100 °C, Chamber 4: 100 °C) in the range of 40 to 120 °C. (3) The appropriately dried coating film on the first film was laminated with a second film (Poly Propylene, PP film) to manufacture a dry film. At this time, the thickness of the dried coating film was set to be in the range of 30 to 60 μm.

[0269] Evaluation Example 1: Measurement of photoreaction rate

[0270] Dry films of each photosensitive resin composition (white solder resist composition (Table 1) and colored solder resist composition (Table 2)) were laminated on FR-4 Cu substrates using a vacuum laminator (CVP-300: manufactured by Nichiko Moulton Co., Ltd.) in the first chamber (60°C, vacuum pressure 3 hPa, press pressure 0.2 MPa, press time 10 sec) and the second chamber (70°C, pressure 6 kgf / cm 2 , and the PET film was laminated and peeled under the conditions of a press time of 20 seconds.

[0271] DI exposure device manufactured by Screen, with an integrated light meter that provides 100 mJ / cm for colors (blue, green, black) 2 , 300mJ / cm for white 2Using a Kodak manufacturing step tablet N0.2 (41-stage) photomask, exposure was performed to 20 to 28 stages, development was performed for 60 seconds with a 1.0% Na2CO3 aqueous solution at 30°C under a spray pressure of 0.2 MPa, and curing was performed for 60 minutes in an oven at 150°C to obtain a cured product (solder resist layer) of the photosensitive resin layer.

[0272] After the first curing was completed, the cured product of the photosensitive resin layer peeled off with a knife was measured for IR on the diamond plate of ATR using FT-IR equipment, and the acrylate peak was confirmed using this IR spectrum, and the degree of curing (photoreaction rate) of the acrylate was measured, which is shown in Table 3.

[0273] [Photoreaction rate calculation method]

[0274] (1) Samples of a composition that was not subjected to the first curing and a cured product that was subjected to the first curing were prepared.

[0275] (2) The uncured composition and the cured product were placed on a diamond plate and FT-IR was measured.

[0276] (3) The acrylate peak (1394-1424 cm) of the cured product is taken as a reference for the uncured composition. -1 ) and calculated the reaction rate by comparing the surroundings (calculation formula below).

[0277] <Photoreaction rate calculation formula: Cured acrylate peak (1394~1424cm -1 ) height / uncured acrylate peak (1394–1424 cm -1 ) height × 100>

[0278] ◎: 70%≤photoreaction rate

[0279] ○: 60%≤photoreaction rate<70%

[0280] △: 50%≤photoreaction rate<60%

[0281] X: Photoreaction rate <50%

[0282] [Sensitivity]

[0283] Dry films of each photosensitive resin composition (white solder resist composition (Table 1) and colored solder resist composition (Table 2)) were laminated on the FR-4 Cu substrate using a vacuum laminator (CVP-300: manufactured by Nichiko Moulton Co., Ltd.) in the first chamber (60°C, vacuum pressure 3 hPa, press pressure 0.2 MPa, press time 10 sec) and the second chamber (70°C, pressure 6 kgf / cm 2 , press time 20 seconds), and then the PET film was peeled off after leaving it at room temperature.

[0284] DI exposure device manufactured by Screen, with a cumulative light meter that measures 100 mJ / cm for colored materials. 2 , 300mJ / cm for white 2 The film was exposed using a Kodak manufacturing step tablet N0.2 (41-stage) photomask, developed for 60 seconds with a 1.0% Na2CO3 aqueous solution at 30°C and a spray pressure of 0.2 MPa, and cured in an oven at 150°C for 60 minutes to obtain a cured film. The gloss level thereof was visually confirmed and shown in Table 3.

[0285] Evaluation Example 2: Measurement of moisture absorption and water vapor permeability

[0286] [Moisture absorption rate]

[0287] The photosensitive resin composition according to the examples and comparative examples was applied on a PET film using a vacuum laminator (CVP-300: manufactured by Nichiko Moulton Co., Ltd.) in the first chamber (60°C, vacuum pressure 3 hPa, press pressure 0.2 MPa, press time 10 seconds) and the second chamber (70°C, pressure 6 kgf / cm 2 , a dry film was produced under the conditions of a press time of 20 seconds and the PET film was peeled off.

[0288] DI exposure device manufactured by Screen, with a cumulative light meter that measures 100 mJ / cm for colored materials. 2 , 300mJ / cm for white 2Using a Kodak manufacturing step tablet N0.2 (41-stage) photomask, exposure was performed to 20 to 28 stages, development was performed for 60 seconds with a 1.0% Na2CO3 aqueous solution at 30°C and a spray pressure of 0.2 MPa, and curing was performed for 60 minutes in an oven at 150°C to obtain a cured product. The moisture absorption rate (water absorption rate) of the dry films produced in the examples and comparative examples was measured according to the ASTM D570 standard test method, and the results are shown in Table 3.

[0289] <Method of measuring moisture absorption>

[0290] (1) Before the test, the sample is dried in an oven at (50±2)℃ for 24 hours.

[0291] (2) For the leftover sample, measure the weight of the sample before moisture absorption (cut the sample of the composition into 2 inches wide and 2 inches long).

[0292] (3) Place the sample whose weight was measured before moisture absorption into a beaker containing purified distilled water and leave it at room temperature for 24 hours.

[0293] (4) After removing the sample left in a moist condition in a beaker containing distilled water, remove any moisture from the surface of the sample and measure its weight.

[0294] (5) Calculate the moisture absorption rate using the weight before and after the test.

[0295] ◎: 0.5%≤ moisture absorption rate < 1%

[0296] ○: 1%≤ moisture absorption rate < 2%

[0297] △: 2%≤ moisture absorption rate < 5%

[0298] X: 5% or more

[0299] [Water vapor transmission rate]

[0300] By repeating the same process as for measuring moisture absorption, a 700 μm thick cured product was obtained. This cured product was placed in a WVTR device and the water vapor transmission rate (WVTR) was measured according to the standard test method of ASTM F1249, and the results are shown in Table 3.

[0301] <Measurement temperature: 38±2℃, humidity 100%, measurement range 0.005~400(g / m 2 day), measurement mode M1, (volume 1cm 3 )>

[0302] ◎: 1 ≤ WVTR (water vapor transmission rate) < 10 (g / m) 2 day)

[0303] ○: 10 ≤ WVTR (water vapor transmission rate) < 20 (g / m) 2 day)

[0304] △: 20 ≤ WVTR (water vapor transmission rate) < 33 (g / m) 2 day)

[0305] X: 33 ≤ WVTR (water vapor transmission rate)

[0306] [Pencil Hardness]

[0307] Using the hardened coating produced in the same manner as the sensitivity evaluation, pencils from B to 9H were ground so that the tip of the lead was flat, about 45 o The hardness of the pencil at which peeling of the film did not occur was recorded by applying pressure at an angle of , and is shown in Table 3.

[0308]

[0309] Referring to Fig. 1 and Table 3, when TMO is included as a photopolymerization initiator, the UV absorption rate in the range of 350 nm to 430 nm is higher than that of other photopolymerization initiators (TPO, TPO-L, Omnipol TP). Due to its high UV absorbance, the TMO photopolymerization initiator has higher sensitivity and photoreactivity at the same exposure dose than other photopolymerization initiators, and when curing a photosensitive composition, it has excellent photoreactivity and photoreactivity, and has excellent curing degree and curing density, so that a harder cured coating film can be formed.

[0310] Referring to FIGS. 2a, 2b, and Table 3, when TMO is included as a photopolymerization initiator, the photoreaction rate is high, so the degree of curing and curing density are increased, and a hard cured coating film is formed, and thus, moisture penetration of the cured coating film is reduced, and moisture absorption is reduced. In addition, the TMO photopolymerization initiator has a similar molecular structure to the TPO photopolymerization initiator, but it has more hydrophobic properties due to the additional inclusion of a methyl group than TPO, making it easy to prevent moisture absorption and penetration.

[0311] Specifically, Examples 3 to 9 and Examples 11 to 18 have higher photoreaction rates than Comparative Examples 1 to 11, and due to this high photoreaction rate, a hard cured coating film is formed, the pencil hardness and surface hardness are high, and the penetration of moisture is prevented by the hard cured coating film, so the water vapor transmission rate and moisture absorption rate are lower. Due to the low water vapor transmission rate and moisture absorption rate, the degree of oxidation and corrosion of copper included in the printed wiring board formed on the cured coating film is very low, and it can be confirmed that there is no phenomenon of peeling, discoloration, or dissolution.

[0312] In addition, in the case of Examples 3 to 9 and Examples 11 to 18, the overall photoreaction rate was high, the sensitivity was high, and the cured film was hard, so the pencil hardness was excellent overall (6H to 8H). However, in the case of Examples 1 and 10, the content of TMO, a photopolymerization initiator, was low, so the photoreaction rate was low, and the surface hardening degree was relatively poor, so the pencil hardness was lower than that of the other examples (5H).

[0313] On the other hand, in Comparative Examples 1 to 4 and Comparative Examples 8 to 11, the overall photoreaction rate was low, resulting in a soft cured film and low pencil hardness. However, in Comparative Examples 5 to 7, the pencil hardness was relatively high (6H) due to the increase in thermal hardening by the thermal curing catalyst.

[0314] Evaluation Example 3: BHAST Test

[0315] The dry films produced in each example and comparative example were laminated on a substrate having a comb-shaped electrode (line / space = 50 μm / 50 μm) formed thereon using a vacuum laminator (CVP-300: manufactured by Nichiko Moulton Co., Ltd.) in the first chamber at 60°C under the conditions of a vacuum pressure of 3 hPa and a vacuum time of 10 seconds, and then pressed under the conditions of a press pressure of 0.2 MPa and a press time of 10 seconds to obtain an evaluation substrate. After peeling off the PET film, the evaluation substrate was measured using a DI exposure device (Screen Co.) with an integrated light meter at 100 mJ / cm in the case of colored films. 2 , 300mJ / cm for white 2The substrate was exposed to light, developed for 60 seconds with a 1% Na2CO3 aqueous solution at 30°C under a spray pressure of 0.2 MPa, and cured in an oven at 150°C for 60 minutes to form a cured film, thereby producing a HAST evaluation substrate. This evaluation substrate was placed in a high-temperature, high-humidity chamber under an atmosphere of 110°C and 85% humidity, charged with a voltage of 20 V, and subjected to a HAST (Highly Accelerated Stress Test) test within the chamber for 250 hours. After 250 hours, the discoloration and dissolution of the cured film of the dry film were evaluated according to the following judgment criteria (Equipment manufacturer: Espec, Ion migration system, Equipment name: NY IM1064). After evaluation, the degree of ion migration, HAST resistance, and adhesion after HAST were confirmed, and additionally, using a spectrophotometer (CM-2600d, Konica Minolta Sensing Co., Ltd.), the reflectance at a wavelength of 450 nm was measured for a cured coating film of 60 μm. Tables 4 and 5 show this.

[0316] [Ion Migration]

[0317] ◎: No ion migration occurs.

[0318] ○: Minor ion migration occurred, but the electrode was not corroded.

[0319] △: A little ion migration occurs, causing the electrode to corrode slightly.

[0320] X: Severe ion migration occurs, causing severe corrosion of the electrode.

[0321] [HAST resistance]

[0322] ○: No discoloration or dissolution.

[0323] △: Discoloration or dissolution is slightly visible to the naked eye.

[0324] X: Discoloration and dissolution are frequently observed with the naked eye.

[0325] [Adhesion after HAST test]

[0326] ○: More than 90% of the checkerboard remains.

[0327] △: Less than 80% to 90% of the checkerboard remains.

[0328] ×: Less than 70% of the board remains.

[0329] [reflectivity]

[0330] ◎: 90%≤reflectivity

[0331] ○: 85%≤reflectivity<90%

[0332] △: 80%≤reflectivity<85%

[0333] X: Reflectance <75%

[0334]

[0335] Referring to FIG. 3 and Table 4, Examples 3 to 9 and Examples 11 to 18 containing the photopolymerization initiator TMO have higher photoreaction rates than Comparative Examples 1 to 11 using other photoinitiators. Due to this, when curing the photosensitive composition with the same exposure dose, the photoreaction is excellent, and the degree of curing and the curing density are increased, so that a hard cured film can be formed. Accordingly, the moisture penetration of the cured film is reduced, so that moisture absorption is reduced. Therefore, even when the BHAST test was performed for 250 hours under high temperature and high humidity conditions, ion migration and electrode corrosion did not occur. In addition, there was no discoloration or dissolution, and there was no major problem with the adhesion when the adhesion test was performed. However, in the case of Examples 1, 2, and 10, the content of TMO was relatively low, so the photoreaction rate was relatively low compared to Examples 3 to 9 and Examples 11 to 18, and the cured film was formed softly, so the adhesion and resistance were relatively low after HAST, and a little dissolution occurred.

[0336] Meanwhile, in Comparative Examples 1 to 4 and Comparative Examples 8 to 11, moisture absorption and penetration increased, ion migration and corrosion of the copper electrodes occurred severely, resulting in discoloration and dissolution, and adhesion problems were also observed. Consequently, when displays or electronic products are exposed to moisture for extended periods, electrode corrosion may occur, potentially affecting long-term reliability.

[0337]

[0338] Referring to Table 5, it can be confirmed that Examples 1 to 4 have higher reflectivity after the HAST test compared to Comparative Examples 1 to 4. Since Examples 1 to 4 have a high photoreactivity and low hygroscopicity and moisture permeability, even when a BHAST evaluation is performed in a high temperature and high humidity environment, moisture absorption and penetration into the cured film (solder resist layer) do not occur easily, so the degree of oxidation and corrosion of copper is very low and there is no discoloration or dissolution.

[0339] Evaluation Example 4: Thermal Analysis and Outgassing Measurement

[0340] [Thermal Analysis Experiment]

[0341] To determine the thermal decomposition temperature of photopolymerization initiators TMO, TPO, Omnipol TP, and TPO-L, a differential calorimeter (e.g., TGA, TGA5500, TA Instruments Inc.) was used. Thermal decomposition temperature T d was obtained by measuring the temperature of 25 to 500℃ using TGA, in an air atmosphere, with a sample weight of 10 to 20 mg, in an aluminum pan (non-airtight), at a heating rate of 10℃ / min. Thermal decomposition temperature T d is the 5% weight loss temperature by thermogravimetric analysis. The 5% weight loss temperature of each initiator was measured according to the following method and is shown in Table 6 below.

[0342] [Outgas content measurement]

[0343] A photosensitive resin composition according to an example or comparative example was laminated on a PET film using a vacuum laminator (CVP-300: manufactured by Nichiko Moulton Co., Ltd.) in a first chamber at 60°C under conditions of a vacuum pressure of 3 hPa and a vacuum time of 10 seconds to produce a dry film, and the PET film was peeled off.

[0344] DI exposure device manufactured by Screen, with a cumulative light meter that measures 100 mJ / cm for colored materials. 2 , 300mJ / cm for white 2 The entire surface was exposed to 23 layers using a Kodak Step Tablet N0.2 (41-layer) photomask. Subsequently, development was performed for 60 seconds with a 1.0% Na2CO3 aqueous solution at 30°C and a spray pressure of 0.2 MPa. After that, the cured product of the photosensitive resin layer was obtained by curing in an oven at 150°C for 60 minutes.

[0345] A powder sample was collected from the fabricated resist layer and placed in a thermal desorption unit (TDU) manufactured by GURSTEL. Specifically, the powder sample was heated at a rate of 30°C to 60°C / min using helium as a purge gas (50 ml / min), heated at 150°C for 60 minutes, and desorbed and collected at -50°C. The collected outgas components were separated and analyzed using a gas chromatography mass spectrometer (8890 / 5977B) manufactured by Agilent Technologies, quantified in n-dodecane conversion, and then the weight % was measured based on the weight of the photopolymerization initiator contained in the cured product of the photosensitive resin layer.

[0346] The measurement conditions for gas chromatography are as follows. Column: Agilent Technologies capillary column DB-1MS (length 30 m, inner diameter 0.25 mm, thickness 0.25 μm), detector: MS (ITQ900), carrier gas: helium, injector temperature: 300°C, detector temperature: 230°C, column temperature conditions: initial temperature 50°C, hold at 50°C for 2 minutes after sample injection, then increase to 300°C at 12°C / sec, hold for 10 minutes after reaching 300°C.

[0347] The outgas content of each example and comparative example was measured according to the following method and is shown in Table 6 below.

[0348] <Method for measuring outgas content>

[0349] The peak of the photopolymerization initiator was identified by analyzing TD-GCMS. At this time, the unit of the peak is expressed as ㎍ / g, which means how many ㎍ of gas is generated per 1g of sample when converted to n-dodecane, and the sum of the outgassing of the photopolymerization initiator peak was measured. At this time, the peak area ratio of the photopolymerization initiator to the area of ​​n-dodecane, which is the reference for GC-MS, was calculated (calculation formula below).

[0350] (Outgas content evaluation)

[0351] ◎: Outgas content <1,000ppm

[0352] ○: 1,000ppm≤outgas content<3,000ppm

[0353] △: 3,000ppm≤outgas content<5,000ppm

[0354] X: 5,000ppm≤outgas content

[0355]

[0356] Referring to Table 6, the photopolymerization initiator TMO has a temperature (T) at which 5% of the composition is decomposed compared to the photopolymerization initiators TPO and TPO-L. d) value is the highest. Therefore, the amount of photopolymerization initiator decomposed at high temperatures is small, and as shown in the comparison of Examples 1, 2, 3, 10, 11 containing a TMO photopolymerization initiator and Comparative Examples 1, 2, 3, 8, 9, 10 containing a different photopolymerization initiator, the content of outgas generated when curing is performed at the same temperature is significantly small.

[0357] If a lot of outgassing occurs, discoloration of the sealing layer may occur, which may cause reliability issues in long-term use when applied to displays or electronic products.

Claims

1. (A) Carboxyl group-containing resin, (B) photopolymerization initiator, and (C) Contains a weapon filler, A photosensitive resin composition, wherein the above (B) photopolymerization initiator comprises at least one moiety represented by the following chemical formula 1. <Chemical Formula 1> In the above chemical formula 1, R 1 is hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted non-aromatic cyclic group or aromatic group having 6 to 20 carbon atoms, R a is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, The substituent of the above substituted alkyl group having 1 to 10 carbon atoms, the substituted non-aromatic cyclic group having 6 to 20 carbon atoms or the aromatic group is an alkyl group having 1 to 10 carbon atoms, * is a bonding site with a neighboring atom.

2. In paragraph 1, A photosensitive resin composition, wherein the above (B) photopolymerization initiator comprises at least one moiety represented by the following chemical formula 1A. <Chemical Formula 1A> R a and R b is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, The substituent of the above substituted alkyl group having 1 to 10 carbon atoms is an alkyl group having 1 to 10 carbon atoms, * is a bonding site with a neighboring atom.

3. In paragraph 1, The above (B) photopolymerization initiator is in a solid state at room temperature (25°C) and has a weight average molecular weight (M w ) is in the range of 350 to 900 g / mol, a photosensitive resin composition.

4. In paragraph 1, The photosensitive resin composition, wherein the photopolymerization initiator (B) has a thermal decomposition temperature of 240°C or higher.

5. In paragraph 1, A photosensitive resin composition, wherein the above (B) photopolymerization initiator is represented by the following chemical formula 2. <Chemical Formula 2> 6. In paragraph 1, A photosensitive resin composition further comprising at least one selected from the group consisting of an oxime photopolymerization initiator, an epoxy resin, an acrylic resin, a thermal curing catalyst, a dispersant, and a colorant.

7. In paragraph 6, A photosensitive resin composition wherein the above-mentioned thermosetting catalyst is at least one selected from the group consisting of imidazole, melamine, and dicyandiamide or a derivative thereof.

8. In paragraph 6, A photosensitive resin composition, wherein the colorant is at least one selected from the group consisting of a white pigment, a black pigment, a blue pigment, and a green pigment.

9. In paragraph 1, A photosensitive resin composition, wherein the content of the photopolymerization initiator (B) is 0.06 to 20 wt% based on the total weight of the composition.

10. In paragraph 1, A photosensitive resin composition having a reflectance of 90% or more at 450 nm when the cured product is cured to a thickness of 60 μm using a spectrophotometer.

11. In any one of paragraphs 1 to 10, A photosensitive resin composition having a moisture absorption rate (water absorption rate) of 5% or less as measured by the method of ASTM D570 for a cured product obtained by curing the photosensitive resin composition.

12. In any one of paragraphs 1 to 10, The moisture vapor transmission rate (WVTR) measured by the ASTM F1249 method for the cured product of the photosensitive resin composition was 33 (g / m 2 ·day) or less photosensitive resin composition.

13. A dry film having a photosensitive resin layer formed by applying and drying a photosensitive resin composition according to any one of claims 1 to 10 on a first film.

14. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 10 or the photosensitive resin layer of a dry film obtained therefrom.

15. A printed wiring board comprising a cured product according to Article 14 as a solder resist.

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