TWI531861B - Photosensitive resin composition with good reliability and method for preparing the same - Google Patents

Description

Photosensitive resin composition with good reliability and preparation method thereof

The present invention relates to a photosensitive resin composition having good reliability and a method for producing the same, and more particularly to a photocurable and thermosetting resin composition capable of forming a cured coating having good flexibility, which ensures the curing coating The layer serves as a solder paste for a semiconductor package and has important properties such as PCT resistance, HAST resistance, resistance to electroless gold plating, and thermal shock resistance; a method of preparing the composition; and a composition The dried film and cured product; and a printed circuit board comprising a cured coating such as a solder resist formed from the composition.

As for the solder resist for a semiconductor package substrate currently used, high resolution, good development properties, high reliability, and the like are required. In particular, in order to ensure high reliability, it is required to be resistant to conditions of high temperature and high humidity. For example, there is a substantial need for techniques to alleviate the stress applied to the flux during PCT (pressure cooker test), HAST (highly accelerated stress test), and TC (thermal cycle). In addition, solder resists should provide stress relief and flexibility depending on the "light-thin-short-small" trend of semiconductor packages. Furthermore, it needs to be at high temperatures and high A technique for suppressing Cu migration of a copper pattern in a circuit board under humidity conditions.

In the conventional solder resist, a butadiene-modified epoxy resin elastomer is used as a stress relieving agent to ensure reliability (for example, Korean Patent Application Laid-Open No. 10-2012-0022820, 10-2011-0102193 No.). However, since the elastomer itself participates in the thermal reaction, the reduction in heat resistance can be caused by a decrease in the glass transition temperature, and it is not easy to control the reactivity of the entire solder resist composition.

Meanwhile, inorganic fillers are used in photosensitive resin compositions which are generally used for printed circuit boards to improve heat resistance and reliability, and a procedure of uniform dispersion is required in order to mix inorganic fillers with raw materials to exhibit good heat resistance. And weather resistance.

In the preparation of a conventional photosensitive resin composition, a roll pulverizer is used to disperse an inorganic filler in a raw material. At this time, physical properties are imparted to the dispersion process when the dispersion process is performed, and the degree of dispersion is changed according to the composition of the resin, and therefore, the characteristics of the photosensitive resin composition become very different, making quality control and program control difficult.

As described above, if the photosensitive resin composition is prepared according to a conventional method using a roll pulverizer, the production time is too long and the productivity is deteriorated, thereby reducing the manufacturing efficiency. Further, during the dispersion process using the roll pulverizer, the product is exposed to the external environment, so the possibility of contamination is high, and there is a high risk of safety accident at work.

In order to solve the conventional problems explained above, the present invention has There is a goal of providing a photocurable and thermosetting resin composition comprising a non-reactive elastomer to increase resin dispersibility and thus form a cured coating having good flexibility while ensuring PCT Resistance, HAST resistance, resistance to electroless gold plating, and thermal shock resistance; a method of preparing the composition; a dried film of the composition and a cured product; and a cured coating (such as by A printed circuit board of the solder resist formed by the composition.

Another object of the present invention is to provide a method for producing a photosensitive resin composition which is preferable because it simultaneously increases the amount of production and improves the stability of the quality by reducing the production time, and also achieves a cost reduction effect.

In order to achieve the above object, the present invention provides a photocurable and thermosetting resin composition comprising: (1) a highly heat-resistant resin containing an unsaturated double bond and a carboxyl group, (2) a photopolymerization initiator, and (3) a reactive diluent containing an unsaturated double bond, (4) a thermosetting component, (5) a filler, (6) an ion adsorbent, and (7) one or more elastomers and polyfluorenes selected from the group consisting of core/shell particles An elastomer of an oxygen elastomer.

Other aspects of the invention provide a solder resist obtained by applying and drying the photocurable and thermosetting resin composition.

Another aspect of the present invention provides a solder resist dried film obtained by applying the photocurable and thermosetting resin composition on a substrate film and drying it.

Another aspect of the invention provides that the light is curable and hot A patterned cured product of a solid resin composition.

Another aspect of the present invention is to provide a printed circuit board comprising a layer of the patterned cured product of the photocurable and thermosetting resin composition.

Another aspect of the present invention provides a method for preparing the photocurable and thermosetting resin composition, comprising the steps of: (1) comprising a highly heat-resistant resin containing an unsaturated double bond and a carboxyl group, and a thermosetting group. And the first raw material mixture of the filler and the organic solvent are wet-mixed together in the mixer; (2) using the bead mill to disperse-mix the wet mixture obtained in the step (1); and (3) in the step (2) A second raw material mixture including a photopolymerization initiator is added to the obtained dispersion mixture, and the resulting mixture is stirred and mixed.

If the photocurable and thermosetting resin composition according to the present invention is used, important properties as a solder resist for a semiconductor package such as PCT resistance, HAST resistance, resistance to electroless gold plating, and heat can be secured. Impact resistance, while forming a cured coating with good flexibility.

Furthermore, if a photocurable and thermosetting resin composition is prepared according to the preferred method proposed by the present invention, it is possible to simultaneously increase the manufacturing content and improve the quality stability by reducing the production time, and also achieve a cost reduction effect. And it is very beneficial.

The invention is described in more detail below.

1. Photocurable and thermosetting resin composition

The photocurable and thermosetting resin composition of the present invention comprises as an essential component: (1) a highly heat-resistant resin containing an unsaturated double bond and a carboxyl group, (2) a photopolymerization initiator, and (3) a reactive double bond of a saturated double bond, (4) a thermosetting component, (5) a filler, (6) an ion adsorbent, and (7) one or more elastomers selected from the group consisting of core/shell particles and polyoxyxene elasticity Body elastomer.

(1) Highly heat-resistant resin containing unsaturated double bonds and carboxyl groups

The highly heat-resistant resins containing an unsaturated double bond and a carboxyl group are preferably those derived from phenol or cresol or a derivative thereof which can ensure high heat resistance. The softening point is preferably from 60 ° C to 120 ° C, and more preferably from 70 ° C to 110 ° C. If the softening point of the highly heat-resistant resin containing an unsaturated double bond and a carboxyl group is lower than 60 ° C, the heat resistance of the composition may be deteriorated, and thus heat resistance of poor quality such as solder heat resistance may be caused. If the softening point is higher than 120 ° C, the viscosity may become too high during the production of the resin, so that poor workability and yield reduction may be caused.

In the highly heat-resistant resin, the unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or a derivative thereof (for example, an acrylate or a methacrylate). Further, in order to obtain good developing properties and form a reactive group with the thermosetting portion, the highly heat-resistant resin preferably contains a carboxyl group derived from a polybasic acid anhydride such as phthalic anhydride, maleic anhydride or the like.

In the present invention, the content of the unsaturated double bond and the carboxyl group is high. Specific examples of the heat-resistant resin may include a phenolic hydroxyl group by using a monocarboxylic acid (for example, (meth)acrylic acid) containing an unsaturated double bond, and a novolak resin of phenol or cresol or a derivative thereof The reaction product of chlorohydrin is reacted, and the produced product is obtained by reacting with a polybasic acid anhydride such as maleic anhydride, phthalic anhydride or the like.

The acid value of the highly heat-resistant resin is preferably from 40 to 150 mgKOH/g, and more preferably from 50 to 130 mgKOH/g. If the acid value of the highly heat-resistant resin is less than 40 mgKOH/g, the properties developed with an alkaline aqueous solution may be poor. If the acid value is more than 150 mgKOH/g, the pattern line developed by the alkaline aqueous solution may become thinner, or in some cases, it may be dissolved and peeled off by the alkaline aqueous solution to distinguish the exposed region from the unexposed region. Therefore it may be difficult to form a normal pattern.

Although the weight average molecular weight of the highly heat-resistant resin varies depending on the skeleton of the basic resin, it is preferably from 2,000 to 150,000, and more preferably from 5,000 to 100,000. If the weight average molecular weight is less than 2,000, the humidity resistance and reliability of the cured coating may become poor after exposure, and may cause a change in appearance (such as shrinkage during development and low resolution). If the weight average molecular weight is more than 150,000, the developing property becomes rather poor, and the storage stability becomes lower, which is undesired.

The content of the highly heat-resistant resin is preferably from 20 to 60% by weight, and more preferably from 30 to 50% by weight, based on the total mass of the composition. If the content of the highly heat-resistant resin is less than 20% by weight based on the total weight of the composition, it is unfavorable because the strength of the coating can be lowered. If the content is more than 60% by weight, it is not good because The processability of the viscosity increase of the composition may be poor, and the processability during the application process may be poor.

(2) Photopolymerization initiator

The photopolymerization initiator is preferably one or more selected from the group consisting of an oxime ester photopolymerization initiator, an α-acetophenone photopolymerization initiator, and a mercaptophosphine oxide photopolymerization initiator. Exemplary structural features of such photopolymerization initiators are shown below.

In the above formula (1), R ¹ represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkanol having 2 to 20 carbon atoms. Or benzylidene; and R ² represents phenyl, alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, alkanol having 2 to 20 carbon atoms or benzamidine base.

In the above formula (2), each of R ³ and R ⁴ independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group having 7 to 12 carbon atoms; and each of R ⁵ and R ⁶ independently represents hydrogen. An atom, an alkyl group having 1 to 6 carbon atoms or an alkyl ether in which both R ⁵ and R ⁶ are combined into a cyclic form.

In the above formula (3), each of R ⁷ and R ⁸ independently represents an alkyl group having a linear or branched chain of 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group having 6 to 12 carbon atoms. Or an aryl group substituted by a halogen atom, an alkyl group or an alkoxy group.

The representative oxime ester photopolymerization initiator represented by the above formula (1) preferably contains a compound of the following formulas (4) and (5).

In the above formula (5), R ⁹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzamidine group, and has 2 to 12 carbon atoms. Alkanol or alkoxy; R ¹⁰ represents phenyl, alkyl having 1 to 12 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, alkanol having 2 to 20 carbon atoms or benzene methyl acyl; and R ¹¹ represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms, an alkanol having 2-20 carbon atoms or benzyloxy And fluorenyl; and R ¹² represents a phenyl group, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkanol having 2 to 20 carbon atoms or a benzhydryl group.

Commercial products of the oxime ester photopolymerization initiator of the above formula (1) may include IRGACURE OXE-01 or IRGADE OXE-02 from BASF, and the like. The oxime ester photopolymerization initiator may be used singly or in combination of two or more.

The representative α-acetophenone photopolymerization initiator represented by the above formula (2) may comprise 2-methyl-1-[(4-methylthio)phenyl]-2-(4-morpholinyl) )-1-propanol, 2-benzyl-2-(dimethylamino)-4-N-morpholinylbutanone, 2-(4-methylbenzyl)-2-(di) Methylamino)-1-(4-morpholinylphenyl)butan-1-one and the like. Commercial products of this α-acetophenone photopolymerization initiator may include IRGACURE 907, IRGACURE 369 or IRGACURE 379 from BASF.

The representative mercaptophosphine oxide-based photopolymerization initiator represented by the above formula (3) may comprise 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis-2,4,6- Trimethylbenzimidyl-phenylphosphine oxide, bis-2,4,4-trimethyl-benzyl-phosphine oxide, and the like. Commercial products of such mercaptophosphine oxide photopolymerization initiators may include IRGACURE TPO or IRGACURE 819 from BASF, and the like.

The content of the photopolymerization initiator is preferably from 0.01 to 30 parts by mass, and more preferably from 0.5 to 15 parts by mass based on 100 parts by mass of the highly heat-resistant resin (1) containing an unsaturated double bond and a carboxyl group. . If light gathers The content of the initiator is less than 0.01 parts by mass (based on 100 parts by mass of the highly heat-resistant resin (1)), which is not preferable because of insufficient photocuring, and peeling or coating properties of the coating ( For example, chemical resistance) is reduced. If the content is more than 30 parts by mass, it is not preferable because the light absorption of the coated surface becomes large, and thus the curing property in the deep portion is lowered.

(3) Reactive diluent containing unsaturated double bonds

The reactive diluent containing an unsaturated double bond used in the present invention is photocured by activation energy irradiation, and the highly heat-resistant resin (1) containing an unsaturated double bond and a carboxyl group is insoluble in an aqueous alkaline solution. In addition, it provides an effect of improving the strength of the cured coating by photocuring, and also improves heat resistance and reliability. For the reactive diluent, a compound having, for example, 2 to 6 unsaturated double bonds in the skeleton may be used (but is not particularly limited), but the flexibility and strength of the cured coating and the reliability of the composition may be used. It varies depending on the number of unsaturated double bonds.

Specific examples of the reactive diluent containing an unsaturated double bond are as follows: caprolactone acrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, dimethylpropane tetraacrylate, trimethyl propyl Alcohol triacrylate, tricyclodecane dimethanol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, dipentaerythritol caprolactone acrylate, and the like.

Commercial products of the above reactive diluents may include PHA, DPCA-30, etc. from Nippon Kayaku, and M200, M300, M600, etc. from Miwon Commercial.

The content of the reactive diluent is 100 parts by mass. The highly thermally resistant resin (1) of the unsaturated double bond and the carboxyl group is preferably from 5 to 100 parts by mass, and more preferably from 10 to 70 parts by mass, based on the total. If the content of the reactive diluent is less than 5 parts by mass based on 100 parts by mass of the highly heat-resistant resin (1), it is not preferable because the photocurable substance is lowered, and after the activation energy is irradiated, It is difficult to develop an alkaline aqueous solution to form a pattern. If the content is more than 100 parts by mass, it is not preferable because the solubility property in the alkaline aqueous solution is lowered.

(4) Thermosetting components

In the present invention, the thermosetting component is used to give thermal resistance to a photocurable and thermosetting resin composition. As the thermosetting component, a general thermosetting component such as a blocked isocyanate compound, benzo can be used. A resin, a cyclic carbonate compound, a polyfunctional epoxy compound, a polyfunctional oxetane compound, or the like. Preferably, a compound having 2 or more cyclic ether or thioether groups in the molecule can be used as the thermosetting component.

Examples of the compound having 2 or more cyclic ether groups in the molecule may include a compound having 2 or more epoxy groups in the molecule - that is, a polyfunctional epoxy compound. Examples of the compound having 2 or more cyclic thioether groups in the molecule may include a polyfunctional episulfide compound.

Examples of the polyfunctional epoxy compound include a bisphenol A polyfunctional epoxy resin, a bisphenol F polyfunctional epoxy resin, a hydrogenated bisphenol A polyfunctional epoxy resin, a brominated polyfunctional epoxy resin, and A halogen-containing polyfunctional epoxy resin, a novolak polyfunctional epoxy resin, a biphenyl polyfunctional epoxy resin, or the like. Commercial product of bisphenol A polyfunctional epoxy resin Contains JER828, JER834 and JER1001 from Japan Epoxy Resins; EPICLON 840, EPICLON 850 and EPICLON 1050 from Dainippon Ink and Chemicals; YD-011, YD-013, YD-127 and YD-128 from Tohto Kasei; from Dow Chemical DER317, DER331, DER661, and DER664; ESA-011, ESA-014, ESA-115, and ESA-128 from BASF; and AER330, AER331, AER661, and AER664 from Asahi Kasei; Commercial products of brominated polyfunctional epoxy resins include JERYL 903 from Japan Epoxy Resins; EPICLON 152 and EPICLON 165 from Dainippon Ink and Chemicals; YDB-400 and YDB-500 from Tohto Kasei; DER 542 from Dow Chemical; Araldite 8011 from BASF; et al. Commercial products of novolak polyfunctional epoxy resins include JER152 and JER154 from Japan Epoxy Resins; EPICLON N-730, EPICLON N-770 and EPICLON N-865 from Dainippon Ink and Chemicals; YDCN-701 from Tohto Kasei and YDCN-704; DEN431 and DEN438 from Dow Chemical; Araldite ECN1235 from BASF, Araldite ECN1273 and Araldite ECN1299; and EPPN-201, EOCN-1020, EOCN-104S and RE-306 from Nippon Kayaku; However, it is not limited to the aforementioned polyfunctional epoxy compound. This polyfunctional epoxy resin may be used singly or in combination of two or more. Preferably, a novolak epoxy resin or a mixture thereof is used.

A commercial product of an episulfide compound having 2 or more cyclic thioether groups in the molecule, comprising from Japan Epoxy Resins YL7000; and YSLV-120TE from Tohto Kasei; et al. An episulfide resin produced by replacing an oxygen atom of an epoxy group in a novolak epoxy resin with a sulfur atom can also be used.

The content of the thermosetting component is preferably from 0.6 to 2.5 equivalents, and more preferably from 0.8 to 2.0 equivalents, per equivalent of the highly heat-resistant resin (1) containing an unsaturated double bond and a carboxyl group. If the thermosetting component corresponds to less than 0.6 equivalent of 1 equivalent of the highly heat-resistant resin (1), it is not preferable because the carboxyl group remains in the composition coating, and heat resistance, alkali resistance, electrical insulation, etc. reduce. If the equivalent is more than 2.5, it is not preferable because the low molecular weight cyclic (thio)ether group remains in the dried coating layer, so that the strength and the like of the coating layer are lowered.

(5) Filler

The photocurable and thermosetting resin composition of the present invention includes a filler to increase the physical strength of the coating and the like. A conventional inorganic or organic filler can be used as the filler, and in particular, an inorganic filler such as barium sulfate, nano-cerium oxide or the like is preferably used. In order to obtain a white appearance or flame resistance, a metal oxide such as titanium oxide or the like or a metal hydroxide such as aluminum hydroxide or the like can be used as a filler.

The content of the filler is preferably 200 parts by mass or less, for example, 0.1 to 150 parts by mass, based on 100 parts by mass of the highly heat-resistant resin (1) containing an unsaturated double bond and a carboxyl group, and more preferably It is 1 to 100 parts by mass. If the content of the filler is more than 200 parts by mass (based on 100 parts by mass of the highly heat-resistant resin (1)), it is not preferable because the viscosity of the composition becomes high, so the workability is deteriorated, and Products with reduced printability or solidification become soft.

(6) Ion sorbent

The photocurable and thermosetting resin composition of the present invention includes an ion adsorbent to suppress generation of ion migration in the cured coating layer under conditions of high temperature and high humidity for a long period of time, but does not hinder viscosity increase and adsorption properties. This is considered to be a property derived from an ion adsorbent that acts as an ion exchanger under acidic conditions (for example, a metal hydroxide). That is, it is generally known that under high temperature and high humidity conditions, the cathode in the copper circuit becomes acidic and the anode becomes alkaline by applying a voltage. In addition, since ions (such as chloride ions) are close to the cathode, it can be understood that the metal hydroxide having an ion exchange function can very efficiently receive a halogen ion (which is a material that causes ion migration), particularly chloride ions, and thus can be long-term Inhibition of ion migration.

Therefore, if an ion sorbent is formulated in a photocurable and thermosetting resin composition, it is possible to capture halogen ions (such as chloride ions) generated by heat or humidity, and to remove impurity ions which adversely affect electrical insulating properties. Ion migration is suppressed and electrical insulation properties are improved. This ion adsorbent is an ion getter having excellent ion exchange properties and heat resistance. It captures the ionic impurities present in the system to control various ion-induced problems, is primarily added to and used by IC molding materials or FPC binders, and provides assistance in improving the reliability of electronic materials.

The ion adsorbent may be used alone or in combination of two or more depending on the type of ionic impurities to be captured. Commercial products of ion adsorbents may include IXE-100, IXE-200, IXE-300, IXE-700F, IXE-770D, IXE-800, IXE-6107, IXEPLAS-A1, IXEPLAS-A2, IXEPLAS-A3 from TOAGOSEI , IXEPLAS-B1 and so on. In the present invention, the metal hydroxide is preferably used as an ion adsorbent, and it is also preferred that they are capable of undergoing zwitterionic exchange. More preferably, a mixture of hydrotalcite and zirconium phosphate is used. It is preferably in the form of fine particles, and the diameter of the fine particles is preferably 1 μm or less, and more preferably 0.5 μm or less.

The content of the ion adsorbent is preferably from 0.01 to 30 parts by mass, more preferably from 0.2 to 30 parts by mass, and still more preferably from 0.5 to 20 parts by mass based on 100 parts by mass of the photocurable and thermosetting resin composition. Share. If the content of the ion adsorbent is significantly larger than the above range, it is not preferable because the viscosity and rheological viscosity reduction of the composition become too high, so that the printability is lowered or the adsorption is deteriorated. If the content is too small, it is not preferable because the effect of suppressing ion migration is reduced.

(7) one or more elastomers selected from the group consisting of core/shell particle type elastomers and polyoxyxene elastomers

The photocurable and thermosetting resin composition of the present invention comprises one or more elastomers selected from the group consisting of core/shell particle type elastomers and polyoxyxene elastomers to improve the flexibility of the coating without reducing curing. The extent (such as glass transition temperature and hardness). Conventional elastomers (such as polybutadiene-modified epoxy resins) or carboxy-terminated butadiene acrylonitrile (CTBN) reduce the degree of curing (such as glass transition temperature) and the like, and thus are not preferable.

The core of the core/shell particle type elastomer is preferably selected from the group consisting of polybutadiene, polyfluorene oxide, styrene butadiene rubber (SBR), and mixtures thereof, and a core compatible polymer can be used as the outer casing. Further, an epoxy resin (such as bisphenol A epoxy resin, bisphenol F epoxy resin, etc.) is preferred.

Commercial products of core/shell particle type elastomers may be included Contains MX-153, MX-257, MX-960, MX-170, MX-136, MX-965, MX-217, MX-416, MX-551, etc. from KANEKA. The elastomeric product of this core/shell particle type may be used alone or in combination of two or more of this core/shell particle type elastomer product.

As the polyoxyxene elastomer, it is preferred to use an epoxy functional polyoxyxene elastomer having a microparticle type having a diameter of from 1 μm to 10 μm. Commercial products of polyoxyxene elastomers may include EP-5500, EP-5518, EP-2600, EP-2601, EP-2720, and the like from Dow Corning Toray. The microporous oxygen elastomer product of this microparticle type may be used alone or in combination of two or more of the microporous oxygen elastomer product of this microparticle type.

The core/shell particle type elastomer or polyoxyxene elastomer is preferably one which is dispersed in the epoxy resin at a high concentration. As the epoxy resin for dispersing the elastomer, bisphenol A epoxy resin, bisphenol F epoxy resin, phenolic novolac epoxy resin, epoxypropylamine epoxy resin or alicyclic ring may be used alone. Oxygen resins, or a combination of two or more, are used. The content of the dispersed elastomer is preferably from 10 to 40 parts by mass, and more preferably from 20 to 40 parts by mass, based on 100 parts by mass of the epoxy resin. If the content of the dispersed elastomer is less than 10 parts by mass based on 100 parts by mass of the epoxy resin, the flexibility of the cured coating layer cannot be improved. If the content is more than 40 parts by mass, the dispersing property becomes poor, and thus the elastomer may be in the presence of a foreign substance in the cured coating layer to cause a poor appearance (elastomer of the core/shell particle type), or the development limit may be lowered. Causes errors during the PCB work process (polyoxyelastomer).

The content of the core/shell particle type elastomer or polyoxyxene elastomer is preferably from 1 to 20% by weight, more preferably from 5 to 15% by weight, based on the total mass of the composition. If the content of the elastomer is less than 1% by weight (based on the total weight of the composition, it is not preferable because the flexibility of the cured coating is insufficient, so that defects may be caused (such as coating due to impact) Layer rupture, etc. If the content is more than 20% by weight, it is not good because the appearance may be poor (because of the non-dispersible elastomer in the surface of the cured coating) and the surface of the coating after the drying process may be glued Adhesive (due to the applied epoxy (core/shell particle type of elastomer)), or development limits may be reduced, causing errors during PCB working procedures (polyoxyelastomers).

(8) Colorant

In addition to the components explained above, it is preferred that the photocurable and thermosetting resin composition of the present invention may further comprise a colorant. As the coloring agent, a paint, a dye, a coloring matter, a color former, or the like can be used, and in terms of reducing the environmental load and the effect on the human body, it is preferred that they do not contain a halogen.

The yellow coloring agent used in the present invention contains an azo-based, diazo-based, condensed azo-based, benzimidazole-based, isoindolinone-based, or anthraquinone-based one, and specific examples thereof are as follows: azo: Pigments yellow 001, 002, 003, 004, 005, 006, 009, 010, 012, 061, 062, 065, 073, 074, 075, 097, 100, 104, 105, 111, 116, 167, 169.

Diazo system: Pigment yellow 012, 013, 014, 016, 017, 055, 063, 081, 083, 087, 126, 127, 152, 170, 172, 174, 176, 188, 198.

The azo system of condensation: pigment yellow 093, 094, 095, 128, 155, 166, 180.

Benzimidazole series: Pigment yellows 120, 151, 154, 156, 175, 181.

Isoindolinone series: pigment yellows 109, 110, 139, 179, 185.

Lanthanide: solvent yellow 163, pigment yellow 024, 108, 147, 193, 199, 222.

The blue coloring agent used in the present invention includes phthalocyanine, lanthanide, etc., and specific examples thereof are as follows: pigment blue 15:00, 15:01, 15:02, 15:03, 15:04, 15 : 06, 16:00, 16:01, 60:00.

In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Although the content of the coloring agent is not particularly limited, it is preferably 10 parts by mass or less, and more preferably 0.1 based on 100 parts by mass of the highly heat-resistant resin (1) containing an unsaturated double bond and a carboxyl group. It is used in an amount of 5.0 parts by mass.

In addition to the above components, the photocurable and thermosetting resin composition of the present invention may further include an additive (for example, an antifoaming agent) conventionally used in a curable resin composition, if necessary. Further, the composition may further include an organic solvent to appropriately adjust the viscosity at the time of application.

A method of using the photocurable and thermosetting resin composition of the present invention is as follows: First, the composition is adjusted with an organic solvent to have a viscosity suitable for the application method, followed by, for example, dip coating, shower coating, and roll coating methods. , bar coating method, screen printing method, curtain coating method, etc. are applied to the substrate The organic solvent contained in the composition is evaporated at a temperature of about 60 to 120 °C. Then, the pattern is formed by selective exposure to activation energy by a patterned mask, the pattern of the mask being formed by contact or non-contact or direct exposure by a laser direct exposure apparatus, followed by alkaline An aqueous solution (0.1 to 3.0% aqueous solution of sodium carbonate) was developed to expose the unexposed areas. The composition of the present invention contains a thermosetting component. Therefore, if heated to a temperature of 130 to 160 ° C, the carboxyl group in the highly heat-resistant resin containing an unsaturated double bond and a carboxyl group may be combined with a thermosetting component (such as having 2 or more cyclic (sulfur) in the molecule. The reaction of the ether group compound results in the formation of a cured coating having good heat resistance, chemical resistance, water absorption resistance, adsorption properties, electrical properties and the like.

Examples of substrates that can be used include printed circuit boards or flexible printed circuit boards having pre-formed circuits thereon, glass fibers impregnated with phenol resin, glass fibers impregnated with epoxy resin, impregnated bismaleimide III Resin glass fiber, copper-clad laminate, polyimide film, PET film, glass substrate, ceramic substrate, wafer substrate, and the like.

After applying the photocurable and thermosetting resin composition of the present invention, a hot air convection drying chamber, an infrared drying chamber, a heating plate, or the like can be used to evaporate the solvent.

After application of the photocurable and thermosetting resin composition of the present invention and drying thereof, the obtained coating is exposed to activating energy radiation. The coating is cured by exposure to activating energy radiation. There is an exposure device for activating energy radiation, including a direct lithography device (for example, a laser direct imaging device that uses a computer-derived CAD data to directly express a pattern with a laser An exposure device having a metal halide lamp, an exposure device having a (super) high pressure mercury lamp, a direct lithography device using an ultraviolet lamp such as an (ultra) high pressure mercury lamp, or the like. As for the range of the activation energy, laser light or light having a maximum wavelength range of 340 to 420 nm can be used, and a gas laser, a solid laser, or both can be used.

Soaking method, leaching method, spraying method, brushing method, etc. can be used as a developing method, and an alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, potassium phosphate, sodium citrate, ammonia, amine or the like can be used. As a developing solution.

In addition to the direct application of the liquid form on the substrate, the photocurable and thermosetting resin composition of the present invention can also be used in the form of a dried film having a film (such as polyethylene terephthalate). A flux-preventing layer formed by applying the composition and drying it. A specific embodiment of using the photocurable and thermosetting resin composition of the present invention as a dried film is as follows.

The dried film has a structure in which a base film, a solder resist layer, and, if necessary, a peelable cover film are laminated in sequence. The solder resist layer is a layer obtained by applying a light curable and thermosetting resin composition developable in an alkaline aqueous solution on a base film or a cover film and drying it. The dried film is formed by forming a solder resist layer on the under film, then laminating a film thereon, or forming a solder resist layer on the cover film, followed by laminating a base film thereon. As the base film, a thermoplastic film (such as a polyester film) having a thickness of 1 to 200 μm can be used. The solder resist layer can be uniformly applied to the base film or the cover film by a blade applicator, a slit coater, a notch coater, a film coater or the like. A photocurable and thermosetting resin composition of 5 to 200 μm is formed by drying it. In the case where a protective layer is formed on a printed circuit board by using a dried film, the cover film is peeled off, and the solder resist layer overlaps with the substrate on which the pattern is to be formed, and they are laminated to each other by using a laminator, resulting in a solder resist layer Formed on the substrate on which the pattern is to be formed. For the solder resist thus formed, the steps of exposure, development, and heat curing explained above can be performed to obtain a cured coating. The base film can be peeled off before or after exposure.

Accordingly, other aspects of the present invention provide a solder resist obtained by applying and drying a photocurable and thermosetting resin composition; by applying a photocurable and thermosetting resin composition on a substrate film and drying it A solder resist dried film obtained; a patterned cured product of a photocurable and thermosetting resin composition; and a printed circuit board comprising a layer of a patterned cured product of a photocurable and thermosetting resin composition.

2. Method for preparing a photocurable and thermosetting resin composition

The photocurable and thermosetting resin composition of the present invention can be prepared by a conventional method. For example, it can be prepared by incorporating the raw material components explained above into a reactor having a stirrer, mixing them by stirring, and dispersing them in a 3-roll mill. In this method, the raw material components may be simultaneously incorporated together or sequentially incorporated one by one. According to a specific embodiment of the present invention, the raw material components other than the elastomer and the filler are first stirred at a low speed (for example, 500 rpm) and mixed, and then an elastomer and a filler are added thereto and mixed and stirred at a high speed (for example, 700 rpm). And after stirring, The mixture was dispersed in a 3-roll mill. After the dispersion, the particle size was examined, and if it was 10 μm or more, the dispersion step was repeated.

Preferably, the photocurable and thermosetting resin composition of the present invention can be prepared by a method comprising the steps of: (1) comprising a highly heat-resistant resin containing an unsaturated double bond and a carboxyl group, a thermosetting component, and a first raw material mixture of the filler is co-wet mixed with the organic solvent in the mixer; (2) a wet mixture obtained in the bead mill dispersion-mixing step (1); and (3) obtained in the step (2) A second raw material mixture including a photopolymerization initiator is added to the dispersion-mixture, and the mixture and the resulting mixture are stirred.

In the above method for preparing a photocurable and thermosetting resin composition, the first raw material mixture, the second raw material mixture or both may contain a reactive diluent, an ion adsorbent, an elastomer, and optionally components such as Colorants (such as pigments, etc.), and preferably they are included in the first raw material mixture. According to a preferred embodiment of the present invention, all of the raw material components other than the photopolymerization initiator may be contained in the first raw material mixture.

The bead mill dispersing device which can be used in the above method for preparing a photocurable and thermosetting resin composition has an outer container and an inner container rotatably combined with the outer container, and a wet mixture of the filler is applied to the outer container and The inner containers are fed between them and dispersed therein by the rotation of the inner container. In this procedure, the filler of the coagulated particle type is dispersed into a uniform size.

In the step (1), wet mixing using a filler of a mixer (for example, a homomixer) is preferably carried out for 20 minutes or longer (for example, 20 minutes to 4 hours). If wet mixing is carried out for less than 20 minutes, then the granules The sub-particles may not be uniform, and the giant particles may remain. The wet mixture obtained in the step (1) preferably has a viscosity of 10,000 cPs (10 rpm, @25 ° C) or less. If the viscosity of the wet mixture is greater than this, it is not preferable because in the subsequent step (2), the mixture in the bead mill dispersing device cannot be smoothly circulated, so the filler can still be in the state of non-dispersed particles. Moreover, the dispersion time becomes longer and the productivity is lowered.

As for the beads used in the bead mill dispersion in the step (2), it is preferred to use zirconia beads having a particle diameter of 0.5 mm to 2 mm, more preferably about 1 mm. The rotational speed of the rotor in the bead mill dispersion in the step (2) is preferably from 5 Hz (400 rpm) to 20 Hz (1600 rpm), and more preferably from 10 Hz (800 rpm) to 15 Hz (1200 rpm). If the rotational speed of the rotor is less than 5 Hz, the filler may still be in the state of undispersed particles. If the rotational speed is greater than 20 Hz, the filler is dispersed, but the resin properties may change due to the possibility of increasing the temperature due to the bead friction. The time during which the bead mill is dispersed is preferably from 20 minutes to 2 hours, more preferably from 50 minutes to 80 minutes. If the bead mill is dispersed for less than 20 minutes, the filler may still be in the state of undispersed particles. If the beads mill is dispersed for more than 2 hours, there may be problems with solvent evaporation and possible changes in resin properties and reduced productivity.

The agitation mixing in the step (3) is preferably carried out for 20 minutes or longer (for example, 20 minutes to 3 hours). If the stirring time is less than this, the photopolymerization initiator is not sufficiently dissolved in the resin, and the additive cannot be uniformly mixed with the dispersed component, resulting in a decrease in the function of the additive. If the stirring time is too long, the productivity is lowered. The final photosensitive resin composition obtained after the step (3) preferably has a viscosity of 20,000 to 25,000 cPs (10 rpm, at 25 ° C).

The invention is illustrated in detail by the following examples and comparative examples. However, the scope of the invention is not limited thereto.

[Examples] Example 1

In a reactor equipped with a stirrer, 400 g of a highly heat-resistant resin containing an unsaturated double bond and a carboxyl group (SR90-B3T4, solid content = 65%, acid value = 57 mgKOH/g, KCC) and a double of 100 g were incorporated. Phenol type A thermosetting component (YD-012, bisphenol A epoxy resin, softening point = 80 ° C, equivalent = 650, Kukdo Chemical), and stirred at 500 rpm for 10 minutes. After stirring, 10 g of a reactive diluent containing an unsaturated double bond (dipentaerythritol hexaacrylate (DPHA), Nippon Kayaku) and 30 g of a photopolymerization initiator (Irgacure 369, an oxime ester photopolymerization start) were added thereto. Agent, BASF), followed by the addition of 2g of yellow colorant (pigment yellow 147, BASF), 6g of blue colorant (pigment blue 16:00, BASF) and 5g of ion sorbent (IXEPLAS, hydrotalcite and A mixture of zirconium phosphate, Toa Gosei) and stirred at 500 rpm for 10 minutes. After stirring, 100 g of core/shell particle type elastomer (MX-170, core: polyfluorene, core content: 25%, dispersion medium: bisphenol A epoxy resin, KANEKA) was added thereto, and stirred at 500 rpm. For 10 minutes, 250 g of filler (B-30, surface treated barium sulfate, D (50) = 0.3 μm, SAKAI) was added in portions from 3 to 6 times. After the addition, the mixture was stirred at a high speed of 700 rpm for 20 minutes. At that time, the temperature inside the heat generated by the high-speed stirring was controlled so as not to exceed 45 °C. After stirring, the mixture was dispersed in a 3-roll mill. After the dispersion, the particle size was examined, and if it was 10 μm or more, the dispersion step was repeated. The prepared photocurable and thermosetting resin composition has a solid content of 75% and a viscosity of 13,000 mPa.s.

Example 2

In addition to the use of a 50g core/shell particle type elastomer (MX-170, core: polyfluorene, core content: 25%, dispersion medium: bisphenol A epoxy resin, KANEKA) as an elastomer, The photocurable and thermosetting resin composition was prepared in the same manner as in Example 1. The prepared photocurable and thermosetting resin composition had a solids content of 73% and a viscosity of 12,500 mPa.s.

Example 3

In addition to the fact that a 100 g core/shell particle type elastomer (MX-136, core: polybutadiene, core content: 25%, dispersion medium: bisphenol F epoxy resin, KANEKA) is used as the elastomer, A photocurable and thermosetting resin composition was prepared in the same manner as in Example 1. The prepared photocurable and thermosetting resin composition had a solids content of 75% and a viscosity of 12,500 mPa.s.

Example 4

A photocurable and thermosetting resin composition was prepared in the same manner as in Example 1 except that 100 g of a polyoxyxene elastomer (EP-2600, Dow Corning Toray) was used as the elastomer. The prepared photocurable and thermosetting resin composition has a solid content of 75% and a viscosity of 13,000 mPa.s.

Example 5

In addition to using 50g of polyoxynene elastomer (EP-2600, Dow Corning Toray) A photocurable and thermosetting resin composition was prepared in the same manner as in Example 1 except for the fact of the elastomer. The prepared photocurable and thermosetting resin composition had a solids content of 73% and a viscosity of 12,500 mPa.s.

Example 6

A photocurable and thermosetting resin composition was prepared in the same manner as in Example 1 except that 100 g of a polyoxyxene elastomer (EP-2601, epoxy functionality, Dow Corning Toray) was used as the elastomer. The prepared photocurable and thermosetting resin composition had a solids content of 75% and a viscosity of 12,500 mPa.s.

Comparative example 1

A photocurable and thermosetting resin composition was prepared in the same manner as in Example 1 except that the elastomer was not used. The prepared photocurable and thermosetting resin composition had a solids content of 74% and a viscosity of 15,000 mPa.s.

Comparative example 2

Light was prepared in the same manner as in Example 1 except that 50 g of ethoxylated polybutadiene (EPOLEAD PB-3600, molecular weight: 5900, acid value: 1 or less, DAICEL) was used as the elastomer. A curable and thermosetting resin composition. The prepared photocurable and thermosetting resin composition had a solids content of 75% and a viscosity of 13,500 mPa.s.

Comparative example 3

In addition to the fact that 50 g of butadiene acrylonitrile (CTBN 1300X8, acrylonitrile content: 17%, CVC) was used as the elastomer, in the same manner as in Example 1. The same method was used to prepare a photocurable and thermosetting resin composition. The prepared photocurable and thermosetting resin composition had a solids content of 75% and a viscosity of 13,500 mPa.s.

As for the photocurable and thermosetting resin compositions prepared in the above Examples and Comparative Examples, the glass transition temperature and the modulus were measured using DMA (Dynamic Mechanical Analysis) according to the JPCA standard. The photocurable and thermosetting resin composition prepared by the particle size measurement has a dispersion of 10 μm or less. Table 1 below shows the blending and measuring glass transition temperatures and moduli of the compositions of the examples and comparative examples.

As can be seen from the results of Table 1 above, Comparative Example 1 was compared with Examples 1 to 3 (elastomers having a core/shell particle type of the composition) and Examples 4 to 6 (the composition having a polyoxyxene elastomer). The composition does not have an elastomer) exhibits a comparable glass transition temperature, but a significantly higher modulus. If the modulus is so high, the coating becomes brittle and defects (such as coating damage) are easily generated during the preparation process. Further, Comparative Examples 2 and 4 (the composition having a general elastomer) showed an equal modulus as compared with Examples 1 to 6, but had a lower glass transition temperature of about 10 °C. This low glass transition temperature inhibits curing and causes poor reliability.

Further, the following tests were conducted to evaluate the efficacy of the photocurable and thermosetting resin compositions of the examples and comparative examples.

The circuit-patterned substrate was subjected to surface treatment, water washing, and drying, and the photocurable and thermosetting resin compositions of the examples and the comparative examples were each applied by screen printing on the front surface of the substrate to provide a drying of about 25 μm. The layer thickness was dried at 80 ° C for 30 minutes. As for the exposure procedure after drying, an exposure apparatus equipped with a high pressure mercury lamp was used, and a sensitivity evaluation was performed using a 41-step tablet (41-step tablet, HITACHI CHEMICAL). The exposure procedure was carried out by using this apparatus, and the product was developed with an aqueous solution of 1% sodium carbonate at 30 ° C for 90 seconds. The optimal exposure conditions are selected by the sensitivity results of the stepper plate (sensitivity = paragraph 6).

Development limit assessment

The composition was applied to the substrate by screen printing, and dried at 80 ° C, then taken out from 30 minutes to 100 minutes, taken out at intervals of 10 minutes, and cooled to room temperature. Decide on the development limit when using 1% sodium carbonate in water When developed at 30 ° C for 90 seconds, the maximum allowable drying time without leaving residue.

Adhesive (TACKY) evaluation

The composition was applied to the substrate by screen printing and dried at 80 ° C for 30 minutes, and cooled to room temperature. On this substrate, the polyester film used for the pattern mask was pressed for 1 minute. When the pattern mask film was peeled off, it was evaluated whether the composition was adhesive to the film according to the following criteria.

○: No transfer after peeling off the film.

△: There was a partial transfer after peeling off the film, and a slight force was required when peeling off the film.

X: There is a transfer after peeling off the film, and a force is required when peeling off the film.

Resolution

The composition was applied to the substrate by screen printing and dried at 80 ° C for 30 minutes, and cooled to room temperature. On the substrate, the polyester film for pattern mask was pressed, exposed by an exposure apparatus equipped with a high-pressure mercury lamp and exposed to 600 mJ/cm ² , developed with an aqueous solution of 1% sodium carbonate at 30 ° C for 90 seconds, and washed with water. Form a pattern. The size of the formed pattern was measured as the resolution.

Solder heat resistance

The composition was applied to the substrate by screen printing and dried at 80 ° C for 30 minutes, and cooled to room temperature. The exposure device includes a substrate by a high-pressure mercury lamp and 600mJ / cm ² and additionally 1100mJ / cm ² exposure. Next, heating was carried out at 150 ° C for 60 minutes to complete the final curing. The substrate thus obtained was immersed in a solder bath set to 260 ° C for 10 seconds. Repeat this immersion 3 times. The appearance change and peeling of the solder resist layer were evaluated with the naked eye according to the following criteria.

○: No change in appearance or peeling.

△: slight appearance change or slight peeling.

X: Severe appearance change and peeling.

Folding durability

The composition was applied to the substrate by screen printing and dried at 80 ° C for 30 minutes, and cooled to room temperature. The exposure device includes a substrate by a high-pressure mercury lamp and 600mJ / cm ² and additionally 1100mJ / cm ² exposure. Next, heating was carried out at 150 ° C for 60 minutes to complete the final curing. It will be folded and unfolded 3 times as obtained at an angle of 90°. The appearance change and peeling of the solder resist layer were evaluated with the naked eye according to the following criteria.

○: No change in appearance or peeling.

△: slight appearance change and slight peeling.

X: Severe appearance change and peeling.

PCT

The substrate obtained from the above procedure was treated with a PCT apparatus (manufacturer: IreTech, model: PCT-80) under conditions of 121 ° C, 100% humidity, 2 atmospheres, and 168 hours, and the coating conditions were evaluated according to the following criteria.

○: No appearance change and no color change and no elution.

△: slight appearance change and partial color change and elution.

X: Severe appearance change and excessive color change and elution.

HAST

On the BT substrate having electrodes (line space: 30 μm), a substrate for evaluation was prepared based on the above procedure. On this substrate, the HAST test was carried out under conditions of high temperature/high humidity of 130 ° C and 85% humidity, and a voltage of 5 V was applied for 168 hours. After 168 hours, the substrate was evaluated according to the following criteria. Insulation resistance.

○: 108 Ω or more.

△: 106 to 108 Ω.

X: 106 Ω or less.

Table 2 below shows the results of the evaluation.

Dry film preparation and evaluation

The photocurable and thermosetting resin compositions of the examples and the comparative examples were each diluted with methyl ethyl ketone and applied on a polyester film (PET film), and dried at 80 ° C for 30 minutes to form a film having a thickness of 25 μm. Solder resist layer. A cover film is laminated thereon to prepare a dried film. Cover film was peeled from the dried preparation of the film on the substrate laminated film was dried, and the substrate by the exposure apparatus provided with a high-pressure mercury lamp and 600mJ / cm ² and ² additionally exposed 1100mJ / cm. Next, heating was carried out at 150 ° C for 60 minutes to complete the final curing. The above items of the substrate thus obtained are evaluated, and Table 3 below shows the results of the evaluation.

As can be seen from the results of the above Tables 2 and 3, the photocurable and thermosetting resin composition of the present invention uses an elastomer which does not lower the degree of curing (such as glass transition temperature), and thus exhibits improved PCT resistance, HAST. Resistance and flexibility. According to this, reliability can be improved (for example, PCT resistance and HAST resistance) while reducing defects during the preparation process (such as coating damage). That is, the photocurable and thermosetting resin composition of the present invention has a good PCT resistance, heat resistance, HAST resistance and additional flexibility which are basically required for the solder resist for a semiconductor package, and thus is very suitable for prevention. Solder and solder paste for thin film packages requiring high reliability.

Further, the following procedure was carried out to compare the productivity of the method of preparing a resin composition using a bead mill and the method of using a 3-roll mill.

Sequence and time for the bead mill program

(1) Incorporation of the first raw material mixture (highly heat-resistant resin, thermosetting component, filler, and solvent) and wet mixing: 4 hours

(2) Bead mill dispersion: 2 hours

(3) Incorporation of the second raw material mixture (all other raw material components) and stirring-mixing: 3 hours

(4) Further adding the composition solvent and mixing: 1 hour

- Total production time (per 400kg): 10 hours

- Final yield: 85%

- Productivity per hour: 34.0kg/hour

3-roller pulverizer sequence and time

(1) Incorporate all raw material components and wet mix: 4 hours

(2) 3-roller pulverizer dispersion (2 passes, 1 pass = 400 kg / 4 hours): 8 hours

(3) Further adding the composition solvent and mixing: 1 hour

- Total production time (per 400kg): 13 hours

- Final yield: 85%

- Productivity per hour: 26.1 kg / hour

Further, each photocurable and thermosetting resin composition was prepared by a method using a bead mill and a 3-roller pulverizer, respectively, and the development limit, sensitivity, resolution, and the like were evaluated according to the same method as above. Adhesion, solder thermal resistance, and PCT resistance, as well as the results of the evaluation shown in Table 4 below.

As can be seen from the results of the above Table 4, if the photosensitive resin composition of the present invention is a composition prepared by a bead mill method, it is possible to obtain the same or similar composition as those prepared by the method using the 3-roll mill. The nature of the production while reducing production time, thus significantly improving productivity.

Claims (17)

A photocurable and thermosetting resin composition comprising: (1) a highly heat-resistant resin containing an unsaturated double bond and a carboxyl group, (2) a photopolymerization initiator, and (3) a reactivity containing an unsaturated double bond Diluent, (4) thermosetting component, (5) filler, (6) ion adsorbent, and (7) elasticity of one or more elastomers selected from the core/shell particle type and the microparticle type polyoxo elastomer a body in which the one or more elastic systems selected from the group consisting of a core/shell particle type elastomer and a microparticle type polysiloxane elastomer are dispersed in an epoxy resin, and the elastomer content is 100 parts by mass of epoxy resin The benchmark is 10 to 40 parts by mass. The photocurable and thermosetting resin composition according to claim 1, wherein in the highly heat-resistant resin containing an unsaturated double bond and a carboxyl group, the unsaturated double bond is derived from acrylic acid or A Acrylic acid or a derivative thereof, and the carboxyl group is derived from a polybasic acid anhydride. The photocurable and thermosetting resin composition according to claim 1, wherein the photopolymerization initiator is one or more selected from the group consisting of an oxime ester photopolymerization initiator and an α-acetophenone light. A polymerization initiator and a mercaptophosphine compound are photopolymerization initiators. The photocurable and thermosetting resin composition according to claim 1, wherein the reactive diluent containing an unsaturated double bond comprises There are 2 to 6 unsaturated double bonds. The photocurable and thermosetting resin composition according to claim 1, wherein the thermosetting component is a compound having 2 or more cyclic ether groups or cyclic thioether groups in the molecule. The photocurable and thermosetting resin composition according to claim 1, wherein the ion adsorbent is a mixture of hydrotalcite and zirconium phosphate. The photocurable and thermosetting resin composition according to claim 1, wherein in the core/shell particle type elastomer, the core is selected from the group consisting of polybutadiene, polyfluorene oxide, and styrene. Butadiene rubber and mixtures thereof, and the outer shell is an epoxy resin. The photocurable and thermosetting resin composition according to claim 1, wherein the microparticle type polyoxyxene elastomer has an epoxy functional polyoxyxene elastomer having a diameter of from 1 μm to 10 μm. The photocurable and thermosetting resin composition of claim 1, further comprising a colorant. A solder resist obtained by applying and drying a photocurable and thermosetting resin composition as described in any one of claims 1 to 9. A solder resist dry film obtained by applying a photocurable and thermosetting resin composition as described in any one of claims 1 to 9 to a substrate film and drying it. A patterned cured product of a photocurable and thermosetting resin composition as described in any one of claims 1 to 9. A printed circuit board comprising a layer of a patterned cured product of a photocurable and thermosetting resin composition as described in any one of claims 1 to 9. A method for producing a photocurable and thermosetting resin composition according to any one of claims 1 to 9, comprising the steps of: (1) including a high heat containing an unsaturated double bond and a carboxyl group; a first raw material mixture of a resistant resin, a thermosetting component and a filler is wet-mixed together with an organic solvent in a mixer; (2) a wet mixture obtained in the bead mill dispersion-mixing step (1); and (3) A second raw material mixture including a photopolymerization initiator is added to the dispersion-mixture obtained in the step (2), and the mixture produced by stirring is mixed. The method of claim 14, wherein the wet mixing in the step (1) is carried out for 20 minutes or longer. The method of claim 14, wherein the bead mill in the step (2) is dispersed for 20 minutes to 2 hours. The method of claim 14, wherein the stirring in the step (3) is carried out for 20 minutes or longer.