JP6092165B2 - Photosensitive resin composition having excellent reliability and method for producing the same - Google Patents

Description

  The present invention relates to a photosensitive resin composition excellent in reliability and a method for producing the same, and more specifically, while ensuring PCT resistance, HAST resistance, electroless gold plating resistance, and thermal shock resistance, which are important as solder resists for semiconductor packages. , A photocurable thermosetting resin composition capable of forming a cured film excellent in flexibility, a method for producing the same, a dry film and a cured product thereof, and a printed wiring board in which a cured film such as a solder resist is formed by these It is about.

  Currently, a solder resist for a semiconductor package substrate to be used is required to have high resolution, high developability, high reliability, and the like. In particular, in order to ensure high reliability, resistance is required under high temperature and high humidity conditions. For example, solder resist is used during PCT (Pressure Cooker Test), HAST (Highly Accelerated Stress Test), and TC (Thermal Cycle) evaluation. Therefore, a technology to relieve the stress that is received is essential. Also, due to the trend toward light and thin semiconductor packages, solder resists must also have stress relaxation and flexibility. Furthermore, there is a need for a technology that can prevent copper migration in the circuit board under high temperature and high humidity conditions.

  In conventional solder resists, there are examples (Patent Documents 1 and 2) in which reliability is ensured by using a butadiene-modified epoxy resin as an elastomer as a stress relaxation agent, but since the elastomer itself is involved in the thermal reaction, the glass transition temperature There is a possibility that heat resistance may be lowered due to sensitivity, and it is not easy to adjust the reactivity of the entire solder resist composition.

  On the other hand, in general, an inorganic filler is used in a photosensitive resin composition used for a printed circuit board in order to improve heat resistance and reliability. In order to exhibit high heat resistance and weather resistance, a step of uniformly dispersing is required.

  When manufacturing a conventional photosensitive resin composition, a roll mill is used to disperse the inorganic filler in the raw material, but depending on the resin composition, when the dispersion process is performed, physical properties and degree of dispersion added Will change. Thereby, the characteristic of the photosensitive resin composition also changes, and there are difficulties in quality control and process control.

  When the photosensitive resin composition is manufactured using a roll mill according to the conventional technique as described above, a considerable amount of manufacturing time is required, resulting in a decrease in production volume, thereby causing a problem of inferior production efficiency. In addition, the roll mill has the disadvantages that the product is exposed to the outside during the dispersion process, the possibility of contamination is high, and there is a high risk of safety accidents in work.

Korean Published Patent Publication No. 10-2012-0022820 Korean Published Patent Publication No. 10-2011-0102193

  The present invention is for solving the above-mentioned problems of the prior art, and by applying a non-reactive elastomer, the resin dispersibility is enhanced, and PCT resistance, HAST resistance, electroless gold plating resistance, and thermal shock resistance are ensured. At the same time, a photocurable thermosetting resin composition capable of forming a cured film having excellent flexibility, a method for producing the same, a dry film and a cured product thereof, and a printing in which a cured film such as a solder resist is formed by these. It is a technical problem to provide a wiring board.

  In addition, the present invention is a very preferable method for producing the photosensitive resin composition, which shortens the production time and increases the production amount, and at the same time improves the quality stabilization and has a cost reduction effect. Providing is another technical issue.

In order to achieve the technical problem described above, the present invention provides:
(1) High heat resistant resin containing unsaturated double bond and carboxyl group, (2) Photopolymerization initiator, (3) Reactive diluent containing unsaturated double bond, (4) Thermosetting component And (5) a filler, (6) an ion adsorbent, and (7) one or more elastomers selected from a core-shell particle-type elastomer and a silicon elastomer, and a photocurable thermosetting resin composition.

  According to the other aspect of this invention, the solder resist obtained by apply | coating the said photocurable thermosetting resin composition and drying is provided.

  According to still another aspect of the present invention, there is provided a solder resist dry film obtained by applying the photocurable thermosetting resin composition to a base film and drying it.

According to yet another aspect of the present invention, patterns of been cured product of the photocurable thermosetting resin composition is provided.

According to yet another aspect of the present invention, a printed wiring board comprising patterns of been cured layer of the photocurable thermosetting resin composition is provided.

  According to still another aspect of the present invention, there is provided a method for producing the photocurable thermosetting resin composition, comprising: (1) a high heat resistant resin containing an unsaturated double bond and a carboxyl group, and thermosetting A step of wet-mixing a primary raw material mixture containing components and fillers with an organic solvent using a mixer; (2) a step of dispersing and mixing the wet mixture obtained in the step (1) using a bead mill; and (3 ) A step of adding a secondary raw material mixture containing a photopolymerization initiator to the dispersion mixture obtained in the step (2) and stirring and mixing is provided.

  When the photocurable thermosetting resin composition according to the present invention is used, PCT resistance, HAST resistance, electroless gold plating resistance, and thermal shock resistance, which are important as a solder resist for semiconductor packages, are secured, and at the same time, excellent flexibility. A film can be formed.

  In addition, if a photocurable thermosetting resin composition is produced by the preferred method presented in the present invention, the production time is shortened and the production amount is increased, and at the same time, the quality stabilization is improved and the cost reduction effect is also achieved. Which can be obtained and is very advantageous.

  Hereinafter, the present invention will be described in more detail.

1. Photocurable Thermosetting Resin Composition The photocurable thermosetting resin composition of the present invention includes (1) a high heat resistant resin containing an unsaturated double bond and a carboxyl group as essential components, and (2) light. A polymerization initiator, (3) a reactive diluent containing an unsaturated double bond, (4) a thermosetting component, (5) a filler, (6) an ion adsorbent, and (7) a core-shell particle type elastomer and silicon It includes one or more elastomers selected from elastomers.

(1) High heat resistant resin containing unsaturated double bond and carboxyl group As the high heat resistant resin containing unsaturated double bond and carboxyl group, phenol or cresol capable of ensuring high heat resistance, or Those derived from the derivatives are preferred, and the softening point is preferably 60 ° C to 120 ° C, more preferably 70 ° C to 110 ° C. When the softening point of the highly heat-resistant resin containing an unsaturated double bond and a carboxyl group is less than 60 ° C., the heat resistance of the composition becomes weak, and there is a risk that defects may occur in heat resistance such as solder heat resistance. Beyond ° C., high viscosity in the resin manufacturing process can cause lack of workability and reduced yield.

  In the high heat resistant resin, the unsaturated double bond is preferably derived from acrylic acid or methacrylic acid, or a derivative thereof (for example, acrylate or methacrylate). In addition, the high heat-resistant resin contains a carboxyl group in order to form a reactive group between excellent developability and a thermosetting part, which is a polybasic acid anhydride such as phthalic anhydride or maleic anhydride. The thing derived from a thing is preferable.

  In the present invention, specific examples of the high heat-resistant resin having an unsaturated double bond and a carboxyl group were obtained by reacting phenolic cresol or phenolic hydroxyl group of a noble lac resin of its derivative with epichlorohydrin. After reacting the product with a monocarboxylic acid containing an unsaturated double bond such as (meth) acrylic acid, the resulting product is reacted with a polybasic acid anhydride such as maleic anhydride or phthalic anhydride. Examples of the resulting resin are listed.

  The acid value of the high heat-resistant resin is preferably 40 to 150 mgKOH / g, more preferably 50 to 130 mgKOH / g. When the acid value of the high heat-resistant resin is less than 40 mgKOH / g, the developability with an alkaline aqueous solution becomes poor, and when it exceeds 150 mgKOH / g, the pattern line becomes thin due to the development with an alkaline aqueous solution. There is no distinction between the unexposed portion and the unexposed portion, and it may be dissolved and peeled off by an alkaline aqueous solution, making it difficult to form a normal pattern.

  The weight average molecular weight of the high heat-resistant resin varies depending on the skeleton of the basic resin, but is preferably 2,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight is less than 2,000, the moisture resistance and reliability of the cured coating film after exposure are inferior, and an external shape change such as shrinkage and low resolution can be brought about during development. On the other hand, if the weight average molecular weight exceeds 150,000, developability is remarkably inferior and storage stability is lowered, which is not preferable.

  The blending amount of the high heat-resistant resin is 20 to 60% by weight, preferably 30 to 50% by weight, based on the total weight of the composition. When the blending amount of the high heat-resistant resin is less than 20% by weight of the total weight of the composition, it is not preferable because it causes a decrease in the strength of the coating film. When it exceeds 60% by weight, the workability is lowered due to an increase in the viscosity of the composition and the coating process. It is not preferable because of a decrease in workability.

(2) Photopolymerization initiator As the photopolymerization initiator, one or more selected from the group consisting of oxime ester photopolymerization initiators, α-acetophenone photopolymerization initiators, and acylphosphine oxide photopolymerization initiators are used. It is preferable to do. Exemplary structures such as these photopolymerization initiators are as shown in the following formulas (1) to (3).

(Wherein 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, an alkanol or benzoyl group having 2 to 20 carbon atoms,
R ² represents a phenyl group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkanol or benzoyl group having 2 to 20 carbon atoms. )

(In the formula, R ³ and R ⁴ each independently represent an alkyl group having 1 to 12 carbon atoms or an arylalkyl group having 7 to 12 carbon atoms,
R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether having two bonded thereto. )

(Wherein R ⁷ and R ⁸ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group having 6 to 12 carbon atoms, a halogen atom, Represents an aryl group substituted with an alkyl group or an alkoxy group.)

  Preferred examples of the oxime ester photopolymerization initiator represented by the formula (1) include compounds represented by the following formulas (4) and (5).

(Wherein 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 benzoyl group, an alkanol group having 2 to 12 carbon atoms, or an alkoxy group;
R ¹⁰ represents a phenyl group, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkanol or benzoyl group having 2 to 20 carbon atoms,
R ¹¹ 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, an alkanol or benzoyl group having 2 to 20 carbon atoms,
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 or benzoyl group having 2 to 20 carbon atoms. )

  Examples of the product of the oxime ester photopolymerization initiator of the formula (1) include IRGACURE OXE-01 or IRGACUREOXE-02 manufactured by BASF. Such oxime ester photopolymerization initiators may be used alone or in combination of two or more.

  Representative α-acetophenone photopolymerization initiators represented by the formula (2) include 2-methyl-1-[(4-methylthio) phenyl] -2- (4-morpholinyl) -1-propanol, 2 -Benzyl-2- (dimethylamino) -4-morpholinobutyrophenone, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one and the like. Examples of such α-acetophenone photopolymerization initiator products include IRGACURE 907, IRGACURE 369, and IRGACURE 379 manufactured by BASF.

  Representative acylphosphine oxide photopolymerization initiators represented by the above formula (3) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-2,4,6-trimethylbenzoyl-phenylphosphine oxide, bis -2,4,4-trimethyl-benzyl-phosphine oxide and the like. Examples of products of such acylphosphine oxide photopolymerization initiators include IRGACURE TPO or IRGACURE 819 manufactured by BASF.

  The blending amount of the photopolymerization initiator is preferably 0.01 to 30 parts by mass, preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the (1) unsaturated double bond and carboxyl group. 15 parts by mass is more preferable. When the blending amount of the photopolymerization initiator is less than 0.01 parts by mass with respect to 100 parts by mass of the above (1) high heat-resistant resin, photocuring is insufficient and the coating film is peeled off or chemical resistance. This is not preferable because the coating film properties of the coating film are deteriorated, and when it exceeds 30 parts by mass, the surface of the coating film is strongly absorbed by light, resulting in a decrease in deep-part curability.

(3) Reactive diluent containing an unsaturated double bond The reactive diluent containing an unsaturated double bond used in the present invention is photocured by irradiation with active energy, and (1) the unsaturated double bond. A highly heat-resistant resin containing a bond and a carboxyl group is insolubilized in an alkaline aqueous solution. Moreover, there exists an effect which improves the intensity | strength of a cured coating film through photocuring, and improves heat resistance and reliability. As such a reactive diluent, any compound containing 2 to 6 unsaturated double bonds in the skeleton can be used without particular limitation, but the number of unsaturated double bonds can be used. Depending on the situation, differences may appear in the flexibility and strength of the cured coating and the reliability of the composition.

  Specific examples of reactive diluents containing unsaturated double bonds include caprolactone acrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, dimethylpropane tetraacrylate, trimethylpropanol triacrylate, Examples include cyclodecane dimethanol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and dipentaerythritol caprolactone acrylate.

  Examples of the reactive diluent products include DPHA and DPCA-30 manufactured by Nippon Kayaku Co., Ltd., and M200, M300, and M600 manufactured by Bigen Shoji Co., Ltd.

  The compounding amount of the reactive diluent is preferably 5 to 100 parts by mass, and 10 to 70 parts by mass with respect to 100 parts by mass of the heat-resistant resin containing (1) the unsaturated double bond and the carboxyl group. More preferred. When the blending amount of the reactive diluent is less than 5 parts by mass with respect to 100 parts by mass of the (1) high heat-resistant resin, the photocurability is lowered, and pattern formation is performed by development with an alkaline aqueous solution after irradiation with active energy. Since it becomes difficult, it is preferable, and when it exceeds 100 mass parts, since the solubility with respect to alkaline aqueous solution will fall, it is not preferable.

(4) Thermosetting component In this invention, in order to provide heat resistance to a photocurable thermosetting resin composition, a thermosetting component is used. Examples of the thermosetting component include general-purpose thermosetting components such as a blocked isocyanate compound, a benzoxazine resin, a cyclocarbonate compound, a polyfunctional epoxy compound, and a polyfunctional oxetane compound. Preferably, the thermosetting component includes a compound having two or more cyclic ether groups or thioether groups in the molecule.

  Examples of the compound having two or more cyclic ether groups in the molecule include a compound having two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound, and two compounds in the molecule. A polyfunctional episulfide compound is mentioned as an example of the compound which has the above thioether group.

  The polyfunctional epoxy compound includes bisphenol A polyfunctional epoxy resin, bisphenol F polyfunctional epoxy resin, hydrogenated bisphenol A polyfunctional epoxy resin, brominated polyfunctional epoxy resin, halogen-free polyfunctional epoxy resin. , Noble rack multifunctional epoxy resins, biphenyl multifunctional epoxy resins, and the like. Bisphenol A polyfunctional epoxy resin products include: JER828, JER834, JER1001 manufactured by Nippon Epoxy Resins; EPICLON840, EPICLON850, EPICLON1050 manufactured by DIC Corporation; YD-011, YD-013, YD-127 manufactured by Toto Kasei Co., Ltd. YD-128; DER317, DER331, DER661, DER664 manufactured by Dow Chemical Company; ESA-011, ESA-014, ESA-115, ESA-128 manufactured by BASF Japan; AER330, AER331, AER661 manufactured by Asahi Kasei Kogyo Co., Ltd. AER664; The brominated polyfunctional epoxy resin products include: JERYL903 manufactured by Nippon Epoxy Resins; EPICLON152, EPICLON165 manufactured by DIC Corporation; YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd .; DER542 manufactured by Dow Chemical; BASF Japan Araldide 8011 made by the company; Noble rack type multifunctional epoxy resin products include JER152 and JER154 manufactured by Nippon Epoxy Resins; EPICLON-730, EPICLON-770 and EPICLON-865 manufactured by DIC Corporation; YDCN-701 and YDCN- manufactured by Tohto Kasei Co., Ltd. 704; DEN431, DEN438 manufactured by Dow Chemical Company; Araldide ECN1235, Araldide ECN1273, Araldide ECN1299 manufactured by BASF Japan; EPPN-201, EOCN-1020, EOCN-104S, RE-306 manufactured by Nippon Kayaku Co., Ltd .; . However, it is not limited only to the polyfunctional epoxy compound mentioned above. Such polyfunctional epoxy resins may be used alone or in combination of two or more. Preferably, a noble rack type epoxy resin or a mixture thereof is used.

  Examples of the episulfide compound product having two or more cyclic thioether groups in the molecule include YL7000 manufactured by Nippon Epoxy Resin Co., Ltd. and YSLV-120TE manufactured by Tohto Kasei Co., Ltd. An episulfide resin in which the oxygen atom of the epoxy group of the noble rack type epoxy resin is changed to a sulfur atom can also be used.

  The blending amount of the thermosetting component is preferably 0.6 to 2.5 equivalents relative to 1 equivalent of the high heat resistant resin containing (1) an unsaturated double bond and a carboxyl group, and 0.8 to 2.0 equivalents are more preferred. (1) When the equivalent of the thermosetting component with respect to 1 equivalent of the high heat resistance resin is less than 0.6, the carboxyl group remains in the composition film, which is not preferable because the heat resistance, alkali resistance, electrical insulation and the like are lowered. If the equivalent exceeds 2.5, a low molecular weight cyclic (thio) ether group remains in the dried coating film, and the strength of the coating film is decreased, which is not preferable.

(5) Filler The photocurable thermosetting resin composition of the present invention may contain a filler in order to increase the physical strength of the coating film. As such a filler, a conventional inorganic or organic filler can be used, and in particular, an inorganic filler such as barium sulfate or nano silica is preferably used. In order to obtain a white appearance and flame retardancy, a metal oxide such as titanium oxide, a metal hydroxide such as aluminum hydroxide, or the like may be used as a filler.

  The blending amount of the filler is preferably 200 parts by mass or less, for example, 0.1 to 150 parts by mass with respect to 100 parts by mass of the heat-resistant resin containing (1) an unsaturated double bond and a carboxyl group. More preferably, it is 1-100 mass parts. When the blending amount of the filler exceeds 200 parts by mass with respect to 100 parts by mass of the (1) high heat-resistant resin, the viscosity of the composition becomes high, workability is inferior, printability is reduced, or a cured product is obtained. It is not preferable because it becomes brittle.

(6) Ion adsorbent The photocurable thermosetting resin composition of the present invention does not inhibit the increase in viscosity and adherence, and causes the occurrence of ion migration in the cured coating over a long period of time under high temperature humidification conditions. An ion adsorbent may be included to suppress. This is considered to originate from the property that an ion adsorbent (for example, metal hydroxide) acts as an anion exchanger under acidic conditions. That is, it is generally known that in a copper circuit under high temperature humidification conditions, the positive electrode becomes acidic and the negative electrode becomes alkaline when a voltage is applied. In addition, since anions such as chloride ions are attracted close to the positive electrode, metal hydroxides that have anion exchange action accommodate halogen ions, especially chloride ions, that are the cause of ion migration in the structure very efficiently. Thus, it is considered that the occurrence of ion migration can be suppressed over a long period of time.

  In this way, if an ion adsorbent is added to the photocurable thermosetting resin composition, halogen ions such as chloride ions generated by heat and moisture can be captured, and impurities that adversely affect electrical insulation. By removing ions, ion migration can be suppressed and electrical insulation can be improved. Such an ion adsorbent is an ion getter that has both excellent ion exchange characteristics and high heat resistance, and traps ionic impurities present in the system and causes various problems caused by ions. It is mainly used by adding to IC sealing materials and FPC adhesives, etc., and helps to improve 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 impurity to be trapped. Commercially available ion adsorbents include IXE-100, IXE-200, IXE-300, IXE-700F, IXE-770D, IXE-800, IXE-6107, IXEPLAS-AI, IXEPLAS-A2, manufactured by Toa Kasei Co., Ltd. IXEPLAS-A3, IXEPLAS-B1, etc. are mentioned. In the present invention, a metal hydroxide is preferably used as the ion adsorbent, and it is also preferable that positive ion exchange is possible. More preferably, a mixture of hydrotalcite and zirconium phosphate is used. The form is preferably a fine particle form, and the fine particle diameter is preferably 1 μm or less, more preferably 0.5 μm or less.

  The compounding amount of the ion adsorbent is preferably 0.01 to 30 parts by mass, more preferably 0.2 to 30 parts by mass, and still more preferably 0 with respect to 100 parts by mass of the photocurable thermosetting resin composition. .5 to 20 parts by mass. If the blending amount of the ion adsorbent is more than the above range, the viscosity and thixotropy of the composition will be too high and the printability may be lowered, or the adhesive force may be lowered. This is not preferable because the ion migration suppressing effect is small.

(7) One or more elastomers selected from core-shell particle type elastomers and silicone elastomers The photocurable thermosetting resin composition of the present invention does not inhibit the degree of curing such as glass transition temperature and hardness, and the coating film In order to improve flexibility, one or more elastomers selected from a core-shell particle type elastomer and a silicon elastomer may be included. Polybutadiene-modified epoxy resin or CTBN (CARBOXYL TERMINATED BUTADIENE ACRYLONITRILE), which is a conventional elastomer, is not preferable because it lowers the degree of curing such as glass transition temperature.

  The core of the core-shell particle type elastomer is preferably selected from polybutadiene, silicon, SBR (styrene butadiene rubber) and a mixture thereof. As the shell, a polymer compatible with the core may be used, and bisphenol A may be used. Epoxy resins such as epoxy resin and bisphenol F epoxy resin are preferred.

  Examples of the core-shell particle-type elastomer product include MX-153, MX-257, MX-960, MX-170, MX-136, MX-965, MX-217, MX-416, MX-551 manufactured by Kaneka Corporation. Is mentioned. Such core-shell particle type elastomer products may be used alone or in combination of two or more.

  As the silicone elastomer, a fine particle type epoxy functional silicone elastomer having a particle diameter of 1 μm to 10 μm may be preferably used. Such silicone elastomer products include EP-5500, EP-5518, EP-2600, EP-2601, EP-2720, etc., manufactured by Toray Dow Corning. Such fine particle type silicon elastomer products may be used alone or in combination of two or more.

  It is preferable to use the core-shell particle type elastomer or silicon elastomer dispersed in an epoxy resin at a high concentration. As an epoxy resin used for dispersion of these elastomers, bisphenol A epoxy resin, bisphenol F epoxy resin, phenol noble rack type epoxy resin, glycidylamino type epoxy resin, finger ring type epoxy resin alone or in combination of two or more kinds. May be used. At this time, the content of the dispersed elastomer is preferably 10 to 40 parts by mass, more preferably 20 to 40 parts by mass with respect to 100 parts by mass of the epoxy resin. When the content of the dispersed elastomer is less than 10 parts by mass with respect to 100 parts by mass of the epoxy resin, the flexibility of the cured film cannot be improved. It may exist as a product and cause poor appearance (core-shell particle type elastomer), or developability margin may be inferior, and a defect may occur during the PCB work process (silicon elastomer).

  The amount of the core-shell particle-type elastomer or silicon elastomer is preferably 1 to 20% by weight, more preferably 5 to 15% by weight based on the total weight of the composition. When the blending amount of the elastomer is less than 1% by weight of the total weight of the composition, the cured film is insufficient in flexibility, and is not preferred due to defects such as film damage due to impact or the like, and when it exceeds 20% by weight, the film is cured. Appearance defects are caused by the undispersed elastomer in the surface of the coating, and the applied epoxy resin causes stickiness of the coating surface after the drying process (core-shell particle type elastomer), or the developability margin is inferior, PCB Defects may occur during the work process (silicon elastomer), which is not preferable.

(8) Colorant The photocurable thermosetting resin composition of the present invention may preferably further contain a colorant in addition to the components described above. Examples of such a colorant include pigments, dyes, pigments, and toning agents, and those that do not contain halogen are preferable from the viewpoint of reducing environmental burden and affecting the human body.

Examples of yellow colorants that can be used in the present invention include azo series, disazo series, condensed azo series, benzimidazole series, isoindolino series, and anthraquinone series, and specific examples thereof are as follows:
Azo: Pigment Yellow 001,002,003,004,005,006,009,010,012,061,062,065,073,074,075,097,100,104,105,111,116,167,169
Disazo: Pigment Yellow 012,013,014,016,017,055,063,081,083,087,126,127,152,170,172,174,176,188,198
Condensed azo type: Pigment Yellow 093, 094, 095, 128, 155, 166, 180
Benzimidazole type: Pigment Yellow 120, 151, 154, 156, 175, 181
Isoindolinone: Pigment Yellow 109, 110, 139, 179, 185
Anthraquinone series: Solvent Yellow 163, Pigment Yellow 024,108,147,193,199,222

Examples of the blue colorant that can be used in the present invention include phthalocyanine series and anthraquinone series, 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 may be used.

  Although there is no restriction | limiting in particular in the compounding quantity of the said colorant, Preferably it is 10 mass parts or less with respect to 100 mass parts of high heat resistant resin containing the said (1) unsaturated double bond and a carboxyl group, More preferably, it is 0. .1 to 5.0 parts by mass.

  The photocurable thermosetting resin composition of the present invention may further contain a component (for example, an antifoaming agent) usually used in the curable resin composition, if necessary, in addition to the components described above. Moreover, in order to adjust the viscosity at the time of composition application | coating suitably, you may further contain the organic solvent.

  The method of using the photocurable thermosetting resin composition of the present invention is, for example, as follows. First, after adjusting the composition to a viscosity suitable for the method of applying with an organic solvent, methods such as dip coating method, flow coating method, roll coating method, bar coating method, screen printing method, curtain coating method, etc. on the substrate The organic solvent contained in the composition is evaporated and dried at a temperature of about 60 to 120 ° C. Thereafter, exposure is selectively performed with active energy through a photomask in which a pattern is formed by a contact method or a non-contact method, or the pattern is directly exposed by a laser direct exposure machine or the like, and an unexposed portion is exposed to an alkaline aqueous solution (0 .1 to 3.0% sodium carbonate aqueous solution) to form a pattern. The composition of the present invention contains a thermosetting component, and when heated at a temperature of 130 to 160 ° C., the carboxyl group and the molecule of the highly heat-resistant resin containing the unsaturated double bond and the carboxyl group. React with a thermosetting component having two or more cyclic (thio) ether groups to form a cured coating film with excellent heat resistance, chemical resistance, moisture absorption resistance, adhesion, electrical properties, etc. Can do.

  Examples of the base material include printed wiring boards and flexible printed wiring boards on which circuits are formed in advance, glass fibers impregnated with phenol resin, glass fibers impregnated with epoxy resin, and glass fibers impregnated with bismaleimide triazine resin. Copper foil laminates, polyimide films, PET films, glass substrates, ceramic substrates, wafer substrates and the like can be used.

  After applying the photocurable thermosetting resin composition of the present invention, a hot-air circulating drying furnace, an infrared drying furnace, a hot plate, or the like can be used for the volatile drying of the solvent.

  After apply | coating the photocurable thermosetting resin composition of this invention and evaporating and drying, it exposes with the active energy with respect to the obtained coating film. The coating is cured by exposure to active energy. Exposure machines used for active energy irradiation include direct writing equipment (for example, laser direct image equipment that directly expresses a pattern with CAD data using a computer), an exposure equipment equipped with a metal halide lamp, and an (ultra) high-pressure mercury lamp. And a direct drawing apparatus using an ultraviolet lamp such as a (super) high-pressure mercury lamp can be used. As for the range of the active energy, laser light and ultraviolet lamp light can be used within a maximum wavelength range of 340 to 420 nm, and either a gas laser or a solid laser can be used.

  The developing method can use a deeping method, a shower method, a spray method, a brush method, etc., and the developer includes potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, Alkaline aqueous solutions such as amines can be used.

  The photo-curable thermosetting resin composition of the present invention is a method of applying the composition directly to a substrate in a liquid state. In addition, a solder resist layer formed by applying the composition to a film such as polyethylene terephthalate and drying it. It can be used in the form of a dry film having The specific example which uses the photocurable thermosetting resin composition of this invention as a dry film is as follows.

  The dry film has a structure in which a base film, a solder resist layer, and if necessary, a peelable cover film to be used are laminated in this order. The solder resist layer is a layer obtained by applying a photocurable thermosetting resin composition that can be developed in an alkaline aqueous solution to a base film or a cover film and drying it. After forming a solder resist layer on the base film, a cover film is laminated, or a solder resist layer is formed on the cover film and a base film is laminated to obtain a dry film. As the base film, a thermoplastic film such as a polyester film having a thickness range of 1 to 200 μm is used. The solder resist layer is dried after the photocurable thermosetting resin composition is uniformly applied to the base film or the cover film in a thickness range of 5 to 200 μm with a blade coater, lip coater, comma coater, film coater or the like. Formed. When manufacturing a protective film on a printed wiring board using dry film, the cover film is peeled off, the solder resist layer and the substrate on which the circuit is formed are stacked, and then laminated using a laminator. A solder resist layer is formed on the substrate on which is formed. A cured coating film can be obtained by subjecting the formed solder resist layer to an exposure step, a development step, and a heat curing step as described above. The base film may be peeled regardless of whether it is before exposure or after exposure.

Therefore, according to another aspect of the present invention, a solder resist obtained by applying and drying the photocurable thermosetting resin composition, and applying the photocurable thermosetting resin composition to a base film. , solder resist dry film obtained by drying, patterns of the cure product of patterns of has been cured and the photocurable thermosetting resin composition of the photocurable thermosetting resin composition A printed wiring board including the layers is provided.

2. Manufacturing method of photocurable thermosetting resin composition The photocurable thermosetting resin composition of this invention can be manufactured by a conventional method. For example, the raw material components described above may be charged into a reactor equipped with a stirrer, stirred and mixed, and then dispersed by a three-roll mill. At this time, all the raw material components may be charged simultaneously or sequentially. According to an embodiment of the present invention, the components excluding the elastomer and the filler are first stirred and mixed at a low speed (for example, 500 rpm), and then the elastomer and the filler are further added thereto, and then the high speed (for example, 700 rpm). ), The mixture is dispersed by a three-roll mill when the stirring is completed. Thereafter, when the dispersion is completed, the level of the particle size is confirmed. When the particle size is 10 μm, the dispersion is repeated.

  Preferably, (1) a step of wet-mixing a primary raw material mixture containing an unsaturated double bond and a carboxyl group-containing high heat-resistant resin, a thermosetting component and a filler together with an organic solvent using a mixer; A step of dispersing and mixing the wet mixture obtained in step (1) using a bead mill; and (3) a second raw material mixture containing a photopolymerization initiator in the dispersion mixture obtained in step (2). The photocurable thermosetting resin composition of the present invention can be produced by a method including the steps of adding and stirring and mixing.

  In the photocurable thermosetting resin composition manufacturing method, optional components such as a reactive diluent, an ion adsorbent, an elastomer, and a colorant such as a pigment are the primary raw material mixture and the secondary raw material mixture. Or it may be contained in both, Preferably it is contained in a primary raw material mixture. According to one preferred embodiment of the present invention, all raw material components except the photopolymerization initiator may be contained in the primary raw material mixture.

  The bead mill disperser that can be used in the method for producing the photocurable thermosetting resin composition, the inner container is rotatably coupled in the outer container, and the filler interposed between the outer container and the inner container is a wet mixture. It is dispersed while being rotated by the inner container. In this process, the granular filler is dispersed into a uniform size.

  In the step (1), it is preferable that the wet mixing of the filler using a mixer (for example, a homomixer) is performed for 20 minutes or longer (for example, for 20 minutes to 4 hours). When the wet mixing time is 20 minutes or less, the particles are not uniform and large particles remain. The viscosity of the wet mixture obtained in the step (1) is preferably less than 10,000 cPs (10 rpm, @ 25 ° C.). If the viscosity of the wet mixture is higher than this, in the subsequent step (2), it becomes difficult to smoothly circulate the mixture in the bead mill disperser, so that there is a problem that the particles remain as they are without being dispersed. Delay and productivity are reduced, which is undesirable.

  In the step (2), the beads used at the time of dispersing the bead mill are preferably zirconia oxide beads having a particle size of 0.5 mm to 2 mm, preferably about 1 mm. In the step (2), the rotational speed of the rotor when the beads mill is dispersed is preferably 5 Hz (400 rpm) to 20 Hz (1600 rpm), more preferably 10 Hz (800 rpm) to 15 Hz (1200 rpm). When the rotational speed of the rotor is less than 5 Hz, there is a problem that the particles remain as they are without being dispersed. When the rotor speed exceeds 20 Hz, the physical properties of the resin may change due to temperature rise due to bead friction even if the filler is dispersed. The bead mill dispersion time is preferably 20 minutes to 2 hours, more preferably 50 minutes to 80 minutes. When the bead mill dispersion time is less than 20 minutes, there is a problem that the particles remain as they are without being dispersed. When the bead mill dispersion time is longer than 2 hours, there is a problem of solvent volatilization and a change in resin characteristics, and productivity is lowered.

  The stirring and mixing in the step (3) is preferably performed for 20 minutes or longer (for example, for 20 minutes to 3 hours). When the stirring time is shorter than this, the photoinitiator is not sufficiently dissolved in the resin and the additive is not uniformly mixed with the dispersion raw material, so that the additive function is lowered. If the stirring time is too long, productivity is lowered. The final photosensitive resin composition obtained after the step (3) preferably has a viscosity in the range of 20,000 to 25,000 cPs (10 rpm, @ 25 ° C.).

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited to these.

Example 1
In a reactor equipped with a stirrer, 400 g of a high heat resistant resin (SR90-B3T4, solid content = 65%, acid value = 57 mgKOH / g, manufactured by KCC) containing an unsaturated double bond and a carboxyl group and a bisphenol A type 100 g of a thermosetting component (YD-012, bisphenol A epoxy resin, softening point = 80 ° C., equivalent = 650, manufactured by National Highway Chemical Co., Ltd.) was added and stirred at 500 rpm for 10 minutes. After stirring, 10 g of a reactive diluent containing an unsaturated double bond (dipentaerythritol hexaacrylate (DPHA), manufactured by Nippon Kayaku Co., Ltd.) and a photopolymerization initiator (Irgacure 369, an oxime ester photopolymerization initiator, BASF Japan) 30 g), 2 g yellow colorant (Pigment Yellow 147, manufactured by BASF Japan), 6 g blue colorant (Pigment Blue 16:00, manufactured by BASF Japan), and ion adsorbent (IXEPLAS, hydrotalcite) And 5 g of a mixture of zirconium phosphate and Toa Gosei Co., Ltd. were added and stirred at 500 rpm for 10 minutes. After the stirring is completed, 100 g of core-shell particle type elastomer (MX-170, core: silicon, core content: 25%, dispersion medium: bisphenol A epoxy resin, manufactured by Kaneka Corporation) is added, and stirred at 500 rpm for 10 minutes. 250 g of filler (B-30, surface-treated barium sulfate, D (50) = 0.3 μm, manufactured by Sakai Co., Ltd.) was added in 3-6 divided portions. After completion of the addition, the mixture was stirred at a high speed of 700 rpm for 20 minutes. At this time, the internal temperature did not exceed 45 ° C. due to heat generated by high-speed stirring. After completion of stirring, the mixture was dispersed with a three-roll mill. When the dispersion was completed, the level of particle size was confirmed, and the dispersion was repeated when the particle size was 10 μm or more. The produced photocurable thermosetting resin composition had a solid content of 75% and a viscosity of 13000 mPa · s.

Example 2
As in Example 1, except that 50 g of core-shell particle type elastomer (MX-170, core: silicon, core content: 25%, dispersion medium: bisphenol A epoxy resin, manufactured by Kaneka Corporation) was used as the elastomer. Thus, a photocurable thermosetting resin composition was produced. The produced photocurable thermosetting resin composition had a solid content of 73% and a viscosity of 12,500 mPa · s.

Example 3
As in Example 1, except that 100 g of core-shell particle type elastomer (MX-136, core: polybutadiene, core content: 25%, dispersion medium: bisphenol F epoxy resin, manufactured by Kaneka Corporation) was used as the elastomer. A photocurable thermosetting resin composition was produced. The produced photocurable thermosetting resin composition had a solid content of 75% and a viscosity of 12500 mPa · s.

Example 4
A photocurable thermosetting resin composition was produced in the same manner as in Example 1 except that 100 g of silicon elastomer (EP-2600, manufactured by Toray Dow Corning) was used as the elastomer. The produced photocurable thermosetting resin composition had a solid content of 75% and a viscosity of 13000 mPa · s.

Example 5
A photocurable thermosetting resin composition was produced in the same manner as in Example 1 except that 50 g of silicon elastomer (EP-2600, manufactured by Toray Dow Corning) was used as the elastomer. The produced photocurable thermosetting resin composition had a solid content of 73% and a viscosity of 12,500 mPa · s.

Example 6
A photocurable thermosetting resin composition was produced in the same manner as in Example 1 except that 100 g of silicon elastomer (EP-2601, Epoxy Functional, manufactured by Toray Dow Corning) was used as the elastomer. The produced photocurable thermosetting resin composition had a solid content of 75% and a viscosity of 12500 mPa · s.

Comparative Example 1
A photocurable thermosetting resin composition was produced in the same manner as in Example 1 except that no elastomer was used. The produced photocurable thermosetting resin composition had a solid content of 74% and a viscosity of 15000 mPa · s.

Comparative Example 2
A photocurable thermosetting resin composition as in Example 1 except that 50 g of epoxidized polybutadiene (EPOLEADPB-3600, molecular weight: 5900, acid value: 1 or less, manufactured by Daicel) was used as the elastomer. Manufactured. The produced photocurable thermosetting resin composition had a solid content of 75% and a viscosity of 13500 mPa · s.

Comparative Example 3
A photocurable thermosetting resin composition was produced in the same manner as in Example 1 except that 50 g of butadiene acrylonitrile (CTBN 1300 × 8, acrylonitrile content: 17%, CVC) was used as the elastomer. The produced photocurable thermosetting resin composition had a solid content of 75% and a viscosity of 13500 mPa · s.

  For the photocurable thermosetting resin compositions produced in the examples and comparative examples, the glass transition temperature and modulus were determined using DMA (DYNAMIC MECHANICAL ANALYSIS) based on the JPCA standard which is a standard. It was measured. Moreover, as a result of evaluating the dispersion degree of the manufactured photocurable thermosetting resin composition with a grindometer, all were 10 μm or less. Table 1 below shows the composition of Examples and Comparative Examples, and the glass transition temperature and modulus measurement results.

  As can be seen from the results in Table 1 above, compared to Examples 1 to 3 which are compositions to which a core-shell particle type elastomer is applied and Examples 4 to 6 which are compositions to which a silicone elastomer is applied, Comparative Examples in which no elastomer is applied No. 1 had the same glass transition temperature but a significantly high modulus. Thus, when the modulus is high, the film becomes brittle, and defects such as film damage occur during the manufacturing process. Further, Comparative Examples 2 and 3 to which a general elastomer was applied had a modulus equal to that of the Example, but the glass transition temperature was about 10 ° C. lower. Such a low glass transition temperature inhibits the degree of cure and induces fragile reliability.

  On the other hand, the following characteristic evaluation was performed with respect to the Example and Comparative Example compositions.

  After the circuit pattern substrate is surface-treated, washed with water and dried, the photocurable thermosetting resin compositions of Examples and Comparative Examples are dried by a screen printing method so that the film thickness is about 25 μm. It was applied to the front surface of and dried at 80 ° C. for 30 minutes. After drying, an exposure apparatus equipped with a high-pressure mercury lamp was used as the exposure equipment for the exposure process. For sensitivity evaluation, a 41-stage tablet (manufactured by Hitachi Chemical Co., Ltd.) was used. The exposure process was performed using this apparatus, and it developed with 30 degreeC and 1-% sodium carbonate aqueous solution for 90 second. The optimum exposure conditions were selected through the sensitivity results of the step tablet (sensitivity = 6 steps).

Evaluation of development margin The composition was applied on a substrate by screen printing, dried at 80 ° C., taken out at intervals of 10 minutes from 30 minutes to 100 minutes, and cooled at room temperature. Thereafter, the development margin was defined as the maximum allowable drying time in which no residue remained when developing at 30 ° C. with a 1% aqueous sodium carbonate solution for 90 seconds.

Evaluation of TACKY The composition was applied on a substrate by screen printing, dried at 80 ° C. for 30 minutes, and then cooled at room temperature. A polyester pattern mask film was pressure-bonded to this substrate for 1 minute, and when the pattern mask film was peeled off, the film was evaluated for whether it was sticky (TACKY) according to the following criteria.
○: When the film is peeled off, there is no transfer. Δ: When the film is peeled off, a part of the transfer is present. When the film is peeled off, a fine force is required. ×: When the film is peeled off, the transfer is present and peeled off. When you need power

Resolution The composition was applied onto a substrate by screen printing, dried at 80 ° C. for 30 minutes, and then cooled at room temperature. A film for pattern mask is pressure-bonded to this substrate, exposed at 600 mJ / cm ² using an exposure machine equipped with a high-pressure mercury lamp, developed for 90 seconds at 30 ° C., 1% sodium carbonate aqueous solution, washed with water, and patterned. Formed. The size of the formed pattern was measured and used as the resolution.

Solder heat resistance The composition was applied on a substrate by screen printing, dried at 80 ° C. for 30 minutes, and then cooled at room temperature. This substrate was exposed at 600 mJ / cm ² using an exposure machine equipped with a high-pressure mercury lamp, and further exposed at 1100 mJ / cm ² . Thereafter, the film was heated at 150 ° C. for 60 minutes for final curing. The substrate thus obtained was immersed in a solder bath set at 260 ° C. for 10 seconds. The dipping process was repeated 3 times. At this time, the external appearance change of the solder resist layer and peelability were visually evaluated according to the following criteria.
○: No external change and peeling Δ: Fine external change and fine peeling ×: Extreme external change and peeling of coating film

Flexibility The composition was applied onto a substrate by screen printing, dried at 80 ° C. for 30 minutes, and then cooled at room temperature. This substrate was exposed at 600 mJ / cm ² using an exposure machine equipped with a high-pressure mercury lamp, and further exposed at 1100 mJ / cm ² . Thereafter, the film was heated at 150 ° C. for 60 minutes for final curing. The substrate thus obtained was folded three times and opened three times. At this time, the external appearance change of the solder resist layer and peelability were visually evaluated according to the following criteria.
○: No external change and peeling Δ: Fine external change and fine peeling ×: Extreme external change and peeling of coating film

PCT
The substrate manufactured through the above steps was treated using a PCT equipment (manufactured by Iretech, model name: PCT-80) under conditions of a temperature of 121 ° C., a humidity of 100%, a pressure of 2 atm, and a time of 168 hours. The state of was evaluated according to the following criteria.
○: No external change, discoloration and elution △: Fine external change, partial discoloration and elution ×: Excessive external change, excessive color change and elution

HAST
An evaluation substrate was manufactured on the BT substrate on which the electrodes (line space: 30 μm) were formed based on the above-described steps. A 5 V voltage was applied to the substrate under high temperature and high humidity conditions of a temperature of 130 ° C. and a humidity of 85%, and HAST evaluation was performed for 168 hours. After 168 hours passed, the evaluation was made according to the following criteria through the insulation resistance value.
○: 108Ω or more △: 106-108Ω
×: 106Ω or less

  The characteristic evaluation results are shown in Table 2 below.

Production and evaluation of dry film The photocurable thermosetting compositions of Examples and Comparative Examples were each diluted with methyl ethyl ketone, then applied onto a polyester PET film, dried at 80 ° C. for 30 minutes, and a thickness of 25 μm. A solder resist layer was formed. A cover film was laminated thereon to produce a dry film. The cover film is peeled off from the manufactured dry film, the film is laminated on the substrate, and then exposed at 600 mJ / cm ² using an exposure machine equipped with a high-pressure mercury lamp as in the above process, and further, 1100 mJ / It was exposed in cm ^2. Thereafter, the film was heated at 150 ° C. for 60 minutes for final curing. The characteristic items of the substrate thus obtained were evaluated, and the results are shown in Table 3 below.

  As can be seen from the results in Tables 2 and 3, the photocurable thermosetting resin composition of the present invention has improved PCT resistance, HAST resistance and flexibility by using an elastomer that does not inhibit the degree of curing such as glass transition temperature. It was done. As a result, defects such as film damage during the manufacturing process were improved at the same time as reliability such as PCT resistance and HAST resistance. That is, the photo-curable thermosetting resin composition of the present invention combines PCT resistance, heat resistance, HAST resistance, and flexibility required for a semiconductor package solder resist, and is highly reliable. It is very suitable for solder resists that require high performance and solder resists for thin film packages.

  On the other hand, in order to compare the productivity of the resin composition manufacturing method using a bead mill and the manufacturing method using a three-roll mill, the following steps were performed.

-Bead mill process sequence and required time (1) First raw material mixture (high heat resistance resin, thermosetting component, filler and solvent) input and wet mixing: 4 hours (2) Bead mill dispersion: 2 hours (3) Second Next raw material mixture (all remaining raw material components) charged and stirred and mixed: 3 hours (4) After additional charging of the correction solvent, mixing: 1 hour ・ Total production time (400 kg standard): 10 hours ・ Final yield: 85 %
-Productivity per hour: 34.0 kg / hr

-3 roll mill process sequence and required time (1) Charge and wet mixing of all raw material components: 4 hours (2) Three roll mill dispersion (2 Pass enforcement, 1 Pass = 400 kg / 4 hours): 8 hours (3) Correction solvent After additional addition, mixing: 1 hour ・ Total production time (400 kg standard): 13 hours ・ Final yield: 85%
-Productivity per hour: 26.1 kg / hr

  In addition, for the photocurable thermosetting resin composition produced by the method using a bead mill and the method using a three roll mill, the development margin, sensitivity, resolution, and stickiness (Tacky) are the same as described above. ) The applicability, solder heat resistance and PCT characteristics were evaluated, and the results are shown in Table 4 below.

  As can be seen from the results in Table 4, if the photosensitive resin composition of the present invention is produced by a method using a bead mill, the composition has the same characteristics as the composition produced by a method using a three-roll mill. In addition, the manufacturing time was shortened and the productivity was remarkably improved.

Claims (15)

(1) High heat-resistant resin derived from phenol or cresol, or a derivative thereof, having a softening point of 60 ° C to 120 ° C and containing an unsaturated double bond and a carboxyl group,
(2) a photopolymerization initiator,
(3) a reactive diluent containing an unsaturated double bond,
(4) thermosetting component,
(5) filler,
(6) an ion adsorbent, and (7) a core-shell particle type elastomer in which the core is selected from polybutadiene, silicon, styrene butadiene rubber and a mixture thereof, and the shell is an epoxy resin; and fine particles having a particle size of 1 μm to 10 μm A photo-curable thermosetting resin composition comprising one or more elastomers selected from:
The core-shell particle-type elastomer or silicon elastomer is a material dispersed in an epoxy resin at a high concentration of 10 to 40 parts by mass with respect to 100 parts by mass of the epoxy resin , separately from the thermosetting component. A photocurable thermosetting resin composition.   The unsaturated double bond of the highly heat-resistant resin containing the unsaturated double bond and the carboxyl group is derived from acrylic acid or methacrylic acid, or a derivative thereof, and the carboxyl group is derived from a polybasic acid anhydride. The photocurable thermosetting resin composition according to claim 1.   The photopolymerization initiator is at least one selected from the group consisting of an oxime ester photopolymerization initiator, an α-acetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator. The photocurable thermosetting resin composition according to 1.   2. The photocurable thermosetting resin composition according to claim 1, wherein the reactive diluent containing an unsaturated double bond contains 2 to 6 unsaturated double bonds.   The photocurable thermosetting resin composition according to claim 1, wherein the thermosetting component is a compound having two or more cyclic ether groups or thioether groups in a molecule.   The photocurable thermosetting resin composition according to claim 1, wherein the ion adsorbent is a mixture of hydrotalcite and zirconium phosphate.   The photocurable thermosetting resin composition according to claim 1, further comprising a colorant.   The solder resist obtained by apply | coating and drying the photocurable thermosetting resin composition of any one of Claims 1-7.   The solder resist dry film obtained by apply | coating the photocurable thermosetting resin composition of any one of Claims 1-7 to a base film, and drying.   The patterned hardened | cured material of the photocurable thermosetting resin composition of any one of Claims 1-7.   The printed wiring board containing the patterned hardened | cured material layer of the photocurable thermosetting resin composition of any one of Claims 1-7. A method for producing the photocurable thermosetting resin composition according to any one of claims 1 to 7,
(1) It is derived from phenol or cresol, or a derivative thereof, and has a softening point of 60 ° C to 120 ° C, a high heat resistant resin containing an unsaturated double bond and a carboxyl group, a thermosetting component, and A step of wet-mixing a primary raw material mixture containing a filler together with an organic solvent using a mixer;
(2) a step of dispersing and mixing the wet mixture obtained in the step (1) using a bead mill; and (3) a step of containing a photopolymerization initiator in the dispersion mixture obtained in the step (2). Introducing the secondary raw material mixture and stirring and mixing;
A method comprising the steps of:   The method according to claim 12, wherein the wet mixing in the step (1) is performed for 20 minutes or more.   The method according to claim 12, wherein the bead mill dispersion in the step (2) is performed for 20 minutes to 2 hours.   The method according to claim 12, wherein the stirring and mixing in the step (3) is performed for 20 minutes or more.