TWI356280B - - Google Patents

Description

1356280 IX. Description of the invention % [Technical field to which the invention pertains] * The present invention relates to a permanent mask suitable for use as a printed wiring board. After exposure, an image is formed by imaging with an aqueous alkaline solution, and then borrowed A photocurable thermosetting resin composition capable of forming a high reflectance solder resist film by heat hardening, and forming a solder resist pattern on the surface of a printed circuit board on which a circuit is formed Printed wiring board. [Prior Art] In general, a printed wiring board is formed by etching an unnecessary portion of a copper foil bonded to a laminated board to form a circuit wiring person, and the electronic component is placed in a predetermined space by soldering. When making such a printed wiring board, a 'resist resist film is generally used. In other words, the solder resist film is used as a circuit protective film when soldering electronic parts. In the solder resist film, in order to prevent the solder from adhering to unnecessary portions, the circuit conductor is prevented from directly being exposed to the air, and reacts with oxygen and moisture. Moreover, it can also function as a permanent protective film for a circuit board. Therefore, the solder resist is required to have properties such as adhesion, electrical insulation, solder heat resistance, solvent resistance, and chemical resistance. In the direction of miniaturization (fineness), multi-layering, and veneering, the mounting method is progressing toward the surface-mounting technology (SMT). Therefore, the anti-welding resist film is also becoming more and more necessary. • To achieve miniaturization, 'high resolution, high precision, and high reliability. A technique for forming such a pattern of a solder resist is, for example, a photoresist method capable of accurately forming a fine pattern. In particular, from the viewpoint of environmental considerations, the photo-resistance method of the alkali-developing type -4- 1356280 has become mainstream. For example, in Patent Document 1 and Patent Document 2, a reaction product obtained by reacting an unsaturated monocarbonic acid with a novolak-type epoxy resin and further adding a polybasic acid anhydride as a base polymer, which can be imaged by an aqueous alkaline solution, is disclosed. Photoresist ink composition. On the other hand, in recent years, a diode (LED) that emits a backlight of a liquid crystal display such as a portable terminal, a computer, a television, or the like, or a light source of a lighting device, is directly mounted on the cover. Use of solder resist film on printed wiring boards. Therefore, in order to utilize the light of the LED very efficiently, a printed wiring board having a high reflectance resistive resist film is being required. [Patent Document 1] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. It is formed using a white photocurable thermosetting resin composition. However, since the white photocurable thermosetting resin composition itself has a high reflectance, it is difficult to sufficiently absorb the light necessary for curing when irradiated with light, and it is difficult to form a pattern latent image correctly. Poor resolution. Accordingly, an object of the present invention is to provide a photocurable thermosetting resin composition capable of forming a high reflectance solder resist film. When light is irradiated, white photohardenable thermosetting of a pattern latent image can be accurately formed. Resin composition - 5 - 1356280 - and a printed wiring board having a high reflectance solder resist film formed using the white photocurable thermosetting resin composition. (Means for Solving the Problem) As a result of careful study by the present inventors, it has been found that a white resin composition having a high reflectance is irradiated by containing at least one oxime ester photopolymerization initiator as a photopolymerization initiator. At the time of light, the pattern latent image can also be formed correctly, and has good resolution. By using a carboxyl group-containing resin containing no aromatic ring and using rutile-type titanium oxide as a white pigment, the photoactivity of the aromatic ring and titanium oxide caused by the resin can be suppressed, and the light can be deteriorated (yellowing) to grow. High reflectivity during the period. In other words, according to the first aspect of the present invention, there is provided a white photocurable thermosetting resin composition comprising (A) a carboxyl group-containing resin not containing an aromatic ring; and (B) at least one type a photopolymerization initiator of an oxime ester photopolymerization initiator; (C) an epoxy compound; (D) a rutile-type titanium oxide; and (E) a diluent. According to another aspect of the present invention, there is provided a printed wiring board which is formed by using a white light-curable thermosetting resin composition according to the first side surface on a surface of a printed wiring board on which a circuit is formed. It is obtained by soldering a resist film. According to the present invention, the present invention can provide a photocurable thermosetting resin composition which can form a high reflectance solder resist film by using as a solder resist, and can form a pattern correctly when irradiated with light. A latent image, a white photohardenable thermosetting resin composition having good resolution and a -6 - 1356280 type having high reflectance resistance resistance formed by using a photocurable thermosetting resin composition Printed wiring board of the film. [Embodiment] (Best Mode for Carrying Out the Invention) Hereinafter, the present invention will be described in further detail. The white photocurable thermosetting resin composition of the present invention contains: (A) a carboxyl group-containing resin not containing an aromatic ring; and (B) a photopolymerization initiator containing at least one oxime ester photopolymerization start (C) epoxy compound; (D) rutile-type titanium oxide and (E) diluent. The carboxyl group-containing resin (A) which does not contain an aromatic ring is a carboxyl group-containing resin having one or more photosensitive unsaturated double bonds, and does not have photosensitivity as long as it is a carboxyl group-containing resin which does not contain an aromatic ring. The carboxyl group-containing resin of the unsaturated double bond can be used, and is not limited to a specific resin. The carboxyl group-containing resin (A) which does not contain an aromatic ring is preferably a carboxyl group-containing resin which is formed from an aliphatic polymerizable monomer. In particular, any of the resins listed below which do not contain an aromatic ring (either oligomer or polymer) can be used. In other words, (1) a carboxyl group-containing resin obtained by copolymerizing unsaturated carbonic acid with a compound having an unsaturated double bond: (2) a carboxyl group-containing (meth)acrylic copolymer resin and one molecule containing an epoxy resin a photosensitive carboxyl group-containing resin obtained by reacting an ethane ring with a compound having an ethylenically unsaturated group; (3) 1. 1356280 compound having one epoxy group and an unsaturated double bond in the molecule, and having an unsaturated double bond The copolymer of the compound is reacted with an unsaturated monocarboxylic acid to form a photosensitive carboxyl group-containing resin obtained by reacting a second-stage hydroxyl group with a saturated or unsaturated polybasic acid anhydride. (4) A photosensitive hydroxyl group obtained by reacting a saturated or unsaturated polybasic acid anhydride with a hydroxyl group-containing polymer, and reacting the resulting carboxylic acid with a compound having one epoxy group and an unsaturated double bond in one molecule. And carboxyl resin. In the above-mentioned (2) photosensitive carboxyl group-containing resin, (a) a carboxyl group-containing (meth)acrylic copolymer resin, and (b) an ethylene oxide ring and ethylene in one molecule. A copolymerized resin having a residue obtained by reacting a compound of a unsaturated group is preferred. The carboxyl group-containing (meth)acrylic copolymer resin (a) is obtained by copolymerizing a (meth) acrylate with a compound having one unsaturated group and at least one carboxyl group in one molecule. The (meth) acrylate constituting the copolymerized resin (a), for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, ( (meth)acrylic acid alkyl esters such as methyl methacrylate and hexyl (meth) acrylate; ethyl 2-hydroxy (meth) acrylate, propyl hydroxy (meth) acrylate, hydroxy (methyl) a hydroxy group-containing (meth) acrylate such as butyl acrylate or denatured 2-hydroxy(meth)acrylic acid lactone; a hydroxyl group (methyl group) such as a lactone-denatured 2-hydroxy(meth)acrylate vinegar Acrylates; dimethyl (meth) acrylate, diethyl ethoxy (meth) acrylate, isooctyloxy (meth) acrylate, methoxy (A) Densitious (meth)acrylic acid glycols such as triethyl acrylate-8-1356280, methoxy (meth) acrylate polyethylene glycol, and the like. These may be used alone or in combination of two or more. In the present specification, '(meth)acrylate refers to the term acrylate and methacrylate, and the same applies to other similar expressions. a compound having one unsaturated group and at least one carboxyl group in one molecule, for example, a chain-extended, denaturized monocarboxylic acid, such as a carboxyl group (methyl group), between acrylic acid, methacrylic acid, an unsaturated group, and carbonic acid Ethyl acrylate, 2-propenyloxyethyl succinic acid, 2-propenyl methoxyethylhexahydroterephthalic acid, an unsaturated monocarboxylic acid having an ester bond by denaturation of a lactone, A denatured unsaturated monocarboxylic acid having an ether bond, or a maleic acid or the like having two or more carboxyl groups in its molecule. These may be used alone or in combination of two or more. (b) a compound having an oxirane ring and an ethylenically unsaturated group in one molecule, as long as it is a compound having an ethylenically unsaturated group and an epoxy ring in one molecule, for example, (methyl) Glycidyl acrylate, hydrazine: - glycidyl methyl (meth) acrylate, methyl 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate Ethyl ester, 3,4-epoxycyclobutyl (meth) acrylate, methyl 3,4-epoxycyclohexyl acrylate, and the like. Among them, methyl 4 4_epoxycyclohexyl C methyl acrylate is preferred. These compounds (b) having an oxirane ring and an ethylenically unsaturated group in one molecule may be used singly or in combination of two or more kinds. The acid value of the carboxyl group-containing resin (A) not containing an aromatic ring must be in the range of 5 Å to 200 mg KOH/g. When the acid value is less than 5 〇 mg K 〇 H / g, it is difficult to remove the unexposed portion with a weakly alkaline aqueous solution -9 - 1356280. When it exceeds 200 mgKOH/g, there is a problem that the water resistance and electrical properties of the cured film are poor. The weight average molecular weight of the carboxyl group-containing resin (A) is preferably in the range of 5,000 to 1,000,000. When the weight average molecular weight is less than 5,000, the dryness of the touch is remarkably deteriorated. On the other hand, when the weight average molecular weight exceeds 100,000, the problem of deterioration in storage stability and storage stability is caused, which is not preferable.

The oxime ester photopolymerization initiator in the photopolymerization initiator (B) containing at least one oxime ester photopolymerization initiator used in the present invention, as long as it has a group represented by the following formula (I) The compound may be a compound, and a compound having a thioxanthone structure is preferred. Such a compound having a thioxanthone structure may, for example, be a compound of the following formula (II). [1] (1) • fsssN—0—H—R2

Ri 0

(wherein R1 represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, or an aryl group, and R2 represents an alkyl group having 1 to 7 carbon atoms or an aryl group). [Chemical 2]

(Π) The photopolymerization initiator contained in the resin composition of the present invention contains an oxime ester photopolymerization initiator of -10- 1356280, and even a white photocurable thermosetting resin composition can be used. When the light is irradiated, the pattern latent image can be correctly formed. The photopolymerization initiator of the present invention may be used alone or in combination with other photopolymerization initiators, in the case of using an oxime ester photopolymerization initiator alone or at least one oxime ester photopolymerization initiator. In the present invention, other photopolymerization initiators which can be used together with the oxime ester photopolymerization initiators include, for example, benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether. Benzene and benzoin alkyl ethers; acetophenone, 2,2-methoxy-2-phenylphenyridinium, 2,2-ethoxy-2-phenylacetophenone, Acetophenones such as 2,2-diethoxy-2-phenylacetophenone, 1,1-chloroacetophenone, etc.; 2-methyl-1-[4-mono(methylthio)phenyl) ] 2- 2-morpholylpropan-1-one, 2-benzyl-2-dimethylamino-1_(4-morpholinophenyl)-butanone-1, 2-(dimethylamino) _2 — [(4-Methylphenyl)methyl]-1—μ-(4-morpholinyl)phenyl]-I-butanone-based aminoalkyl phenones; 2-methyl oxime a quinone such as 2-ethyl hydrazine, 2-tert-butyl fluorene or 1-cyclopropene; a ketal such as acetophenone dimethyl ketal or benzyl dimethyl ketal; Diphenyl ketones such as diphenyl ketone; xanthone; (2.6-dimethoxybenzylidene)-2,4,4-pentylphosphine oxide, double (2.6.6) Methyl benzhydryl)-phenylphosphine oxide, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, ethyl-2,4,6-trimethylbenzylidene Phosphine oxides such as phenyl phosphate; various peroxides; titanocene initiators. The other photopolymerization initiators used in the above-mentioned oxime-based photopolymerization initiator may be used singly or in combination of two or more. -11 - 1356280 The photopolymerization initiator (B) containing at least one oxime ester photopolymerization initiator of the present invention may also be combined with N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethyl A photosensitizer such as isopropyl benzoate, pentyl-4-dimethylamino benzoate, tertiary amine such as triethylamine or triethanolamine is used. The photopolymerization initiator (B) containing at least one oxime ester photopolymerization initiator is blended in an amount of from 1 to 30 with respect to 1 part by mass of the carboxyl group-containing resin (A) which does not contain an aromatic ring. The mass fraction is preferably 2 to 25 parts by mass. When the amount of the photopolymerization initiator (B) containing at least one oxime ester-based photopolymerization initiator is less than 1 part by mass, the photocurability is lowered. After the exposure and development, pattern formation becomes difficult. So not good. On the other hand, when it exceeds 30 parts by mass, the thick film hardenability is lowered, and it is also a cause of cost, which is not preferable. Next, as the epoxy compound (C), various epoxy resins can be used, and examples thereof include bisphenol S type epoxy resin, diglycidyl terephthalate, and triglycidyl isocyanurate (for example, Nissan Chemical Co., Ltd. TEPIC-H (holding the structure of three epoxy groups bonded in the same direction for the s-triazine ring bone lattice), and TEPIC (/3 body and holding for In the case of the S-triazine ring skeleton, a heterocyclic epoxy resin or a double is bonded to a mixture of two other epoxy groups in a different direction from the other two epoxy groups. An epoxy resin which is insoluble in a diluent such as a xylenol type epoxy resin, a bisphenol type epoxy resin or a tetraglycidyl xylene sulfhydryl ethane resin, and a bisphenol oxime type epoxy resin and a hydrogenated bisphenol oxime Epoxy resin, bisphenol F resin, brominated bisphenol A epoxy resin, phenol novolak type or cresol novolak type epoxy resin, alicyclic epoxy resin, -12- 1356280 bisphenol A Novolak type epoxy resin, chelating type aldehyde type epoxy resin, amine-containing epoxy resin, rubber denatured cyclopentane Epoxy resin which is soluble in a diluent such as a phenol-based epoxy resin or a polyfluorene-modified epoxy resin-modified epoxy resin, may be used singly or in combination of two or more. The compounding amount of the epoxy resin compound (C) is preferably 5 to 70 parts by mass of the carboxyl group-containing resin (A)' which does not contain an aromatic ring, and more preferably 5 to 60 parts by mass. When the epoxidation multiplying amount exceeds 70 parts by mass, the unexposed portion of the developing liquid is low, and development residual is liable to occur, which is difficult in practical use, and when it is less than 5 parts by mass, the carboxyl group-containing resin (A) should be used. Since the state remains, it becomes difficult to obtain sufficient electrical characteristics, solder heat resistance, and chemical resistance. The epoxy group of the carboxyl group-containing resin (C) which does not contain an aromatic ring (C) is reacted by ring-opening polymerization, and is dissolved in the diluent (E) or other substances in the composition due to drying. Hot, it is easy to crosslink. Therefore, the crosslinking reaction is carried out, and when the drying time is extended, the use of the hard fat alone or the poorly soluble epoxy resin and the easily soluble cyclic resin is one of the characteristics of the present invention using the rutile-type titanium oxide (D). Since anatase type titanium oxide has a higher whiteness than rutile, it is more commonly used. However, due to photocatalytic activity, there are sometimes photocurable thermosetting oxyresin, ethylene epoxide, diester, and emulsifiable fat. The solubility of 100 parts by mass of these rings is preferably (C). On the other hand, the carboxyl group is epoxidized with a group which does not cure the coating film, but when an easy-to-use epoxy resin is used, it is preferably a white pigment which is a type of titanium oxide, and is preferably a white pigment. The resin in the titanium oxide type titanium oxide resin composition-13-1356280 produces discoloration. On the other hand, the rutile-type titanium oxide has a whiteness which is inferior to that of the anatase type, but has little photoactivity, and a stable solder resist film can be obtained. For the rutile-type titanium oxide (D), a known rutile type can be used. Specifically, TR-600, TR-700, TR-75 0, and TR-840 manufactured by Fuji Titanium Industrial Co., Ltd., and 5-500, 11-5 8 manufactured by Ishihara Sangyo Co., Ltd. can be used. 0, 11-63 0, 11-820, 〇11-50, CR-60, CR-90; KR-270, KR-3 1 0 'KR-3 80, etc. manufactured by Titanium Industry Co., Ltd. The amount of the rutile-type titanium oxide (D) is preferably 50 to 300 parts by mass, more preferably 60 to 260 parts by mass, per 1 part by mass of the carboxyl group-containing resin (A) not containing an aromatic ring. good. When the amount is more than 300 parts by mass, the photocurability is lowered and the depth of hardening is lowered, which is not preferable. On the other hand, if it is less than 50 parts by mass, the shielding force is small, and a high reflectance solder resist film cannot be obtained. When the cerium oxide particles (F) are used in the present invention, a photocurable thermosetting resin composition having a deeper depth of hardening can be obtained. This phenomenon is presumed to be due to the fact that the refractive index of cerium oxide is relatively close to that of the carboxyl group-containing resin (A) which does not contain the aromatic ring.

Such a cerium oxide particle (F) can be used by a known person. For example: spherical cerium oxide (ADMAFINE® SO-E1, SO-E2, SO-E5, etc., manufactured by Admatechs), micronized cerium oxide, amorphous cerium oxide, crystalline oxidized oxidized, cerium dioxide Wait. These cerium oxide particles may be used singly or in combination of two or more. The amount of the cerium oxide particles (F) is preferably 50 to 200 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (A - 14 - 1356280) containing no aromatic ring. The diluent (E) used in the present invention may be a photopolymerizable monomer and/or an organic solvent. The photopolymerizable monomer is, for example, an alkyl hydroxyacrylate such as 2-hydroxyethyl acrylate or 2-butyl hydroxyacrylate; or a glycol such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol or propylene glycol. Mono or dipropylene acrylates; N,N-dimethyl decylamine, propylene amide such as N-methylol acrylamide; amines such as N,N-dimethylamino acrylate Alkyl propylene phthalate: a polyol such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol or hydroxylated hydroxy isocyanate or such ethylene oxide or propylene oxide adduct Polyacrylates; phenoxy acrylates, bisphenol A diacrylates, and acrylates of such phenolic ethylene oxide or propylene oxide additions; glyceryl diglycidyl ether, trimethylol An acrylate of a glycidyl ether such as propane triglycidyl ether; a melamine acrylate; and/or a methacrylate corresponding to the above acrylate. • On the other hand, organic solvents such as ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosolve and ethyl cellosolve , butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate, acetic acid Esters such as butyl ester, cellosolve acetate, diethylene glycol monoethyl ether acetate, and esterified esters of the above glycol ethers; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; octane and oxime An aliphatic hydrocarbon such as an alkane; a petroleum solvent such as petroleum ether, petroleum brain, petroleum brain, solvent petroleum brain, or the like. -15- 1356280

The diluent (E)' as described above may be used singly or in combination of two or more. It is preferred to use 20 to 300 parts by mass of a diluent based on 100 parts by mass of the carboxyl group-containing resin (A) not containing an aromatic ring. The purpose of the above-mentioned diluent is not only to make the photopolymerizable monomer easy to apply, but also to dilute the active energy ray-curable resin to enhance photopolymerization: on the other hand, the organic solvent is dried. For filming. Therefore, depending on the diluent to be used, it is possible to use a contact method in which the photomask is in contact with the coating film, or a non-contact type of exposure. Further, in the white photocurable thermosetting resin composition of the present invention, by including an oxidation preventing agent and a hindered amine light stabilizer, thermal deterioration and photodegradation can be further reduced. The oxidation preventive agent is preferably a hindered phenol compound, although it is not particularly limited. Examples of hindered phenolic compounds include NOCRAC® 200, NOCRAC® M-17, NOCRAC® SP, NOCRAC® SP-N, NOCRAC®-NS-5 'NOCRAC®-NS-6, NOCRAC®-NS-30, NOCRAC ®300, NOCRAC®NS-7, NOCRAC®DAH (all of which are manufactured by Ouchi Emerging Chemical Industry Co., Ltd.): MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK A0616, MARK AO-63 5. MARK AO-65 8. MARK AO-15 MARK AO-18, MARK 328, MARK AO-37 (all of the above are manufactured by ADEKA Gas Chemical Co., Ltd.); IRGANOX® 245 , IRGANOX® 259, IRGANOX® 565, IRGANOX® 1010 ' IRG ANOX® 1 03 5, IR G AN Ο X ® 1 0 7 6, IRGANOX® 1 08 1 , IRGANOX® 1 098, IRGANOX® 1 222, IRGANOX® 1330 , IRGANOX® 1245WL (all of which are manufactured by-16- 1356280 CIBA Speciality Chemical Co., Ltd.)

Hindered amine light stabilizers such as TINUVIN® 622LD, TINUVIN® 144, CHIMASSORB 944LD, CHIMASSORB 119FL (all manufactured by CIBA Speciality Chemicals); MARK LA-57, LA-62, LA-67, LA-63, LA -68 (all of the above are manufactured by ADEKA Gas Chemical Co., Ltd.); SANOL® LS-770, LS-765, LS-292, LS-2626, LS-1114, LS-744 (all of which are Sangong Life Technology Co., Ltd. manufactures) and so on. The oxidation preventing agent and the photosensitizer are preferably added in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (A) having no aromatic ring. Further, if necessary, a curing accelerator, a thermal polymerization inhibiting agent, a tackifier, an antifoaming agent, a flat agent, a coupling agent, a flame retardant auxiliary agent, or the like can be used. The white photocurable thermosetting resin composition of the present invention can be provided in the form of a liquid or a paste. The white photocurable thermosetting resin composition of the present invention may be diluted as necessary to adjust the viscosity of the coating method. The resin composition is melt-coated on a printed wiring board forming a circuit by a screen printing method, a curtain coating method, a spray coating method, a roll coating method, or the like, for example, at a temperature of 70 to 90 ° C. The organic solvent contained in the composition is volatilized and dried to form a non-stick coating film. Thereafter, the unexposed portion is exposed through a selective active energy source through a photomask, and the unexposed portion is developed by an aqueous alkaline solution to form a photoresist pattern, whereby the printed wiring board of the present invention can be obtained. The aqueous alkali solution of -17 to 1356280 used herein is generally a 0.5 to 5% by weight aqueous sodium carbonate solution, but other basic aqueous solutions may also be used. The other alkaline aqueous solution may, for example, be an aqueous alkaline solution such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium phosphate, sodium citrate, ammonia or an amine. For the illumination source for exposure, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp or a metal halide lamp can be used. Other laser rays can also be used as active light. In order to improve the heat resistance of the solder resist film obtained as described above, it is preferable to perform secondary hardening of the solder resist film by heat of 100 to 20 (TC, ultraviolet rays or far infrared rays. The photocuring property of the present invention is used. The solder resist film formed of the thermosetting resin composition has high reflectance and has properties such as heat resistance, solvent resistance, and electrical properties required for the solder resist film. The solder resist formed by the present invention The resist film also maintains a high reflectance after the accelerated deterioration test. [Examples] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto. Synthesis of a carboxyl group-containing resin containing no aromatic ring: In a 2 liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropper, and a nitrogen introduction tube, 90 g of a solvent of diglyme and 21.4 g of a polymerization initiator were added. - Butyl peroxide - 2 - ethyl acrylate (18- 1356280 PERBUTYL®0, manufactured by Nippon Oil & Fats Co., Ltd.) ' Then heated to 90 ° C. After heating, 3 09.9 g of methacrylic acid, 116_4 g Methyl methacrylate, And 109 g of lactone-denatured 2-hydroxyethyl methacrylate (PLACCEL® FM1 manufactured by DAICEL Chemical Industry Co., Ltd.), bis (4-t-butylene ring) with 2 1 · 4 g of polymerization initiator Peroxydicarbonate (PEROYL® TCP, manufactured by Nippon Oil & Fats Co., Ltd.), which was added dropwise over 3 hours, and further matured over 6 hours to obtain a copolymerized resin containing a carboxyl group. The reaction was carried out in a nitrogen atmosphere. Next, 363.9 g of methyl 3,4-epoxycyclohexyl acrylate (CYCLOMER® A200 manufactured by DAICEL Chemical Co., Ltd.) and 3.6 g of the obtained carboxyl group-containing copolymer resin were added. Cyclobenzyl dimethylamine, 1.80 g of a polymerization inhibitor of hydroquinone monomethyl ether, and then heated to 1 ° C, and the ring-opening addition reaction of the epoxy resin by stirring. After 16 hours A solution having a solid content of 53.8 wt% of a solid content of 108.9 mg KOH/g and a weight average molecular weight of 25,000 and containing no aromatic ring-containing carboxyl group-containing resin was obtained. Hereinafter, this reaction solution is referred to as A-1 varnish. ~6, Comparative Examples 1 to 6 Comply with Table 1 and Table 2, mix and stir The ingredients, dispersion using a three-roll, respectively, made of light-curing a thermosetting resin composition. Digital table are parts by mass. -19-1356280 [Table i]

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 A-1 varnish 186 186 186 186 186 186 R820 180 180 180 180 180 180 828 37 37 37 37 37 37 SO-E5 110 110 110 110 110 110 starter 1 1 1 1 1 1 starter 2 1 starter 3 9 18 starter 4 9 9 18 starter 5 9 9 9 18 monomer 15 15 15 15 15 15 KS-66 3 3 3 3 3 3 Solvent 20 20 20 20 20 20 [Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 A-1 varnish 186 186 186 186 186 186 R820 180 180 180 180 180 180 828 37 37 37 37 37 37 SO-E5 110 110 110 110 110 110 starter 1 starter 2 starter 3 19 38 starter 4 19 38 starter 5 19 38 monomer 15 15 15 15 15 15 KS -66 3 3 3 3 3 3 Solvent 20 20 20 20 20 20 R820 : Rutile type titanium oxide 82 manufactured by Ishihara Sangyo Co., Ltd. 8: Bisphenol A type epoxy resin made of Japanese epoxy resin -20- 1356280 SO-E5 : Adomatech spheroidal cerium oxide initiator 1 : 2 · ( ethoxylated iminomethyl) sulfonium-9-one (oxime ester photopolymerization initiator) Initiator 2: CIBA Spe Тty Chemical OXE02 (Oxime Ester Photopolymerization Initiator) Initiator 3 : CIBA Specialty Chemical IRGACURE 907 Initiator 4: CIBA Specialty Chemical IRGACURE 369 Starting Qi J J : CIBA Specialty Chemical DAROCUR TOP Single Body: Dipentaerythritol hexaacrylate KS-66: Silicone oil solvent manufactured by Shin-Etsu Silicon: carbitol acetate In order to investigate the properties of the solder resist film formed by using each photocurable thermosetting resin composition, The following tests were evaluated. (1) Resolution The screen printing method uses a 100 mesh polyester twill fabric plate to print each light on a laminated board of FR-4 bonded copper foil of l〇〇mmxl50mm size and thickness 1.6mm. The curable thermosetting resin composition was dried at a temperature of 80 ° C for 10 minutes in a hot air circulating drying oven at a film thickness of 40 / zm. Further, the photocurable thermosetting resin composition was overprinted on the respective coating films in the same manner, and dried at 80 ° C in a hot air circulating drying oven for 20 minutes. Using a printed wiring board, HMW-68 0GW' manufactured by Exposure Oak Co., Ltd. and using a mask pattern of -21 - 1356280 80ym and 100/zm lines, ultraviolet light exposure was performed at an accumulated light amount of 500 mJ/cm2. Thereafter, at 30 ° C, a 1% sodium carbonate aqueous solution was used as a developing agent, and the image was developed by a developing machine using a printed wiring board for 60 seconds, followed by 60 minutes at 150 ° C in a hot air circulation type. The test piece was produced by heat hardening in a drying furnace. The line width remaining on the test piece was confirmed, and the resolution was evaluated. The results are shown in Tables 3 and 4. Among them, those with a residual line of 80/zm are ◎, the line with 100//Π1 remains, and the line with 100#m is not left, indicated by X. [Table 3] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Resolution ◎ ◎ ◎ 〇 ◎ 〇 [Table 4]

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Resolution XXXXXX It is understood from Table 3 that the photocuring thermosetting of the present invention containing at least one oxime ester-based photopolymerization initiator is used. In Examples 1 to 6 of the resin composition, it was found that good resolution was obtained. On the other hand, Comparative Examples 1 to 3 which do not contain the oxime ester-based photopolymerization initiator in Table 4 contain the same amount of the starter as the photopolymerization starting dose contained in the Example, but the image was developed. After that, * wireless residual, it can be seen that it does not have good resolution. Therefore, in Comparative Examples 4 to 6, a double amount of photopolymerization initiator was used for the purpose of improving the resolution, but even in such a case, after the development, there was no line residue -22-1356280. stay. (2) Light resistance is printed by pattern printing on a laminated board of FR-4 bonded copper foil of l〇〇mmx 150mm and thickness of 1.6mm using a 100-mesh polyester twill fabric plate by a screen printing method. Each of the photocurable thermosetting resin compositions was dried at 40 ° C for 30 minutes in a hot air circulating drying oven at a film thickness of 40 / zm. The HMW-6 80 GW manufactured by the exposure machine oak was fabricated using a printed wiring board, and exposed to ultraviolet light at a cumulative light amount of 500 mJ/cm 2 to leave a negative pattern of 30 mm squares. Then, at 30 ° C, a 1% sodium carbonate aqueous solution was used as a developing agent, and a developing machine using a printed wiring board was used for image development for 60 seconds, followed by 60 minutes at 150 ° C for hot air circulation. The test piece for the characteristic test was performed by heat-hardening in the drying oven. The obtained test piece was measured by the color-color difference meter CR-400 by the Minolta company. Thereafter, light of 50 J/cm 2 , 100 J/cm 2 , and 150 J/cm 2 was irradiated in a UV conveyor belt furnace (output 150 W/cm metal halide lamp cold mirror) to accelerate deterioration. The results are shown in Table 5 and Table 6. -23- 1356280

[Table 6]

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Initial 値Y 75.15 72.90 72.80 72.80 66.77 73.26 L* 88.04 88.40 88.35 88.35 85.39 88.57 a* 0.32 0.60 0.57 0.59 0.92 0.44 b* 4.02 4.22 2.96 3.05 6.74 3.09 Irradiation 150 J/cm2 Y 69.11 71.48 78.83 68.13 60.37 67.81 L* 86.56 87.72 86.42 86.07 82.04 85.91 a* 1.21 0.90 0.89 0.99 1.48 1.09 b* 5.89 6.52 4.32 11.24 14.67 9.57 △ E*ab 2.55 2.42 2.38 8.51 8.63 7.03 Visual evaluation ◎ ◎ ◎ XXX

[Table 5] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Initial 値Y 77.06 78.29 79.17 76.24 77.24 76.82 L* 90.36 90.91 91.31 89.97 90.43 90.24 a* 0.33 0.03 0.53 0.05 0.72 0.52 b* 3.96 3.02 4.26 3.97 4.63 3.46 Irradiation 150 J/cm2 Y 72.15 72.90 72.80 75.11 74.37 77.35 L* 89.52 89.68 90.95 88.94 89.10 89.19 a* 0.82 0.67 0.08 0.13 0.93 0.39 b* 3.18 3.39 3.16 4.40 5.96 3.50 AE*ab 1.25 1.44 1.24 1.12 1.89 1.06百 评价 ◎ ◎ ◎ ◎ ◎ In Table 5, Y represents the reflectance of the XYZ color system, and L* represents the brightness of the L*a*b color system. a* is the red direction; -a* is the green direction; b* is the yellow direction; -b* is the blue direction, and the closer to zero, the lower the chroma. △ E*ab indicates the change in color. The smaller this point, the smaller the change in color. For the visual evaluation item, the mark ◎ does not feel the change of color -24- 1356280; the △ mark indicates a slight discoloration, and the X mark indicates that there is a noticeable discoloration 〇: It can be clearly seen from Table 5 that the composition of the present invention is used. Implementation of the object. In Examples 1 to 6, even after accelerated deterioration, the reflectance did not decrease significantly. Low, the change in brightness was small, and the △ E * ab ' of the change in color was small. Even in the visual evaluation item, there was no discoloration at all or almost no discoloration. φ As can be seen from Table 6, in Comparative Examples 4 to 6 using the double amount of photopolymerization initiator of the examples, after the accelerated deterioration, the reflectance Y and the lightness L* simultaneously became very low enthalpy, and the change in color was indicated. The △ E*ab's 値 is also very large. In the visual evaluation, it was also confirmed to have discoloration. From this fact, it is understood that even if a double amount of the photopolymerization initiator is used, not only the resolution is not improved, but also the light resistance is poor. (3) Heat resistance φ On each of the test pieces prepared in the same manner as in (2), a rosin-based flux was applied in a solder bath at 260 ° C for 1 sec. Thereafter, it was washed with propylene glycol monomethyl ether acetate, and after drying, it was subjected to a pull-off test by a transparent tape, and the peeling of the coating film was evaluated. The results are shown in Tables 7 and 8. Here, the 〇 mark indicates that peeling of the coating film did not occur, and the X mark indicates that peeling of the coating film occurred. (4) Solvent resistance Each test piece prepared in the same manner as in (2) was immersed in propylene glycol mono-25-1356280 methyl ether acetate for 30 minutes, and dried, and then subjected to a pull-off test using a transparent tape. The peeling and discoloration of the coating film were evaluated. The results are shown in Table 7 and Table 8. Here, the 〇 mark indicates that peeling and discoloration of the coating film did not occur, and the X mark indicates that peeling of the coating film and discoloration occurred. (5) Pencil hardness test A pencil having a flat B to 9H was rubbed on a test piece prepared in the same manner as in (2), and pressed at an angle of about 45° to record peeling of the coating film. The hardness of the pencil. The results are shown in Table 7 and Table 8. (6) Insulation resistance test A test piece was produced under the same conditions as in (2) except that the comb-shaped electrode B sample of the IPC B-25 test pattern was used instead of the FR-4 copper-clad laminate. On this test piece, a bias voltage of DC 5 00 V was applied, and the insulation resistance 値 was measured. The results are shown in Table 7 and Table 8. -26- 1356280 [Table 7] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Heat resistance 〇〇〇〇〇〇 Solvent resistance 〇〇〇〇〇〇 Pencil hardness test 7H 7H 7H 7H 7H 7H Insulation resistance test (Ω) lxlO13 or more lxlO13 or more lxlO13 or more lxlO13 or more lxlO13 or more lxlO13 or more [Table 8] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Heat resistance 〇〇〇〇〇〇 Solvent resistance 〇〇〇〇〇〇 pencil hardness test 7H 7H 7H 7H 7H 7H Insulation resistance test ( Ω ) lxlO13 or more 5x1 012 1 X 1 0 13 or more lxlO13 or more lxlO13 or more lxlO13 The above is known from Table 7 'Using the light of the present invention In Examples 1 to 6 of the curable thermosetting resin composition, 'there are excellent heat resistance, solvent resistance, adhesion, and electrical insulation required for the solder resist film. From the above results, it is known that by containing an oxime ester photopolymerization initiator in the photopolymerization initiator, good light resistance, heat resistance, solvent resistance, adhesion, and electrical insulation can be maintained. In the state of nature, high resolution is also obtained. As described above, according to the present invention, it is possible to obtain a white photocurable thermosetting resin composition which can form a high reflectance solder resist film from -27 to 1356280. The white photocurable thermosetting resin composition of the present invention can form a pattern latent image correctly when irradiated with light, and has good resolution.

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Claims (1)

1356280 Patent Application No. 096138698 Revised Patent Application Scope of the Chinese Patent Application September 15th, 2015. Patent Application Area 1. A white photocurable thermosetting resin composition, characterized by: (A) no aromatic ring a carboxyl group-containing resin; (B) a starter agent containing at least one oxime ester photopolymerization initiator; an epoxy compound; (D) rutile-type titanium oxide; and (E) a dilution, the aforementioned rutile type The amount of the titanium oxide (D) is 50 to 300 in terms of 100 parts of the carboxyl group-containing resin (A) containing no aromatic ring. 2. The white photocurable thermal resin composition of the first aspect of the patent application, wherein The above-mentioned carboxyl group-containing tree which does not contain an aromatic ring is: (a): (meth)acrylic copolymerization containing a carboxyl group; and (b): having an oxirane ring and an ethylenic group in one molecule The carboxyl group-containing copolymer resin obtained by the reaction. 3. The white photocurable thermal resin composition according to the first aspect of the invention, wherein the carboxyl group-containing tree containing no aromatic ring is a carboxyl group-containing resin produced from an aliphatic polymerizable monomer. 4. The white photocurable thermal resin composition according to the first aspect of the invention, wherein the oxime ester photopolymerization initiator is a ketone structure. 5. The white photohardenability according to claim 1 A resin composition further containing (F) 矽. particles. 6. If you apply for any of the scope of items 1 to 4 of the patent scope, modify its special light; (C 丨 ;; mass amount of hardening) (A resin saturated hardening (A hardened thiophene p hardening. White 1356280 The photocurable thermosetting resin composition, wherein the photocurable thermosetting resin composition is a solder resist composition. 7. A printed wiring board characterized by: a printed wiring board on which a circuit is formed On the surface, a white photocurable thermosetting resin composition of the first to fifth aspects of the patent application is used to form a solder resist film. -2-