WO2011125821A1 - 熱硬化性樹脂組成物及びプリント配線板 - Google Patents
熱硬化性樹脂組成物及びプリント配線板 Download PDFInfo
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- WO2011125821A1 WO2011125821A1 PCT/JP2011/058179 JP2011058179W WO2011125821A1 WO 2011125821 A1 WO2011125821 A1 WO 2011125821A1 JP 2011058179 W JP2011058179 W JP 2011058179W WO 2011125821 A1 WO2011125821 A1 WO 2011125821A1
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- WIPO (PCT)
- Prior art keywords
- resin composition
- thermosetting resin
- aromatic ring
- carboxyl group
- epoxy compound
- Prior art date
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Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
- C08L101/08—Carboxyl groups
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/20—Details of printed circuits not provided for in H05K2201/01 - H05K2201/10
- H05K2201/2054—Light-reflecting surface, e.g. conductors, substrates, coatings, dielectrics
Definitions
- the present invention provides a high-reflectance white thermosetting resin composition suitable as an insulating layer for a printed wiring board on which a light-emitting element such as a light-emitting diode (LED) is mounted, and an insulating layer made of a cured product of the composition. It is related with the printed wiring board which has.
- a light-emitting element such as a light-emitting diode (LED)
- printed wiring boards have been increasingly used by being mounted directly on LEDs that emit light at low power, such as backlights for liquid crystal displays of portable terminals, personal computers, televisions, etc., and light sources of lighting fixtures (for example, JP, 2007-249148, A (paragraphs 0002-0007)).
- the insulating film that is formed as a protective film on the printed wiring board is not only the characteristics required for the solder resist film, such as solvent resistance, hardness, solder heat resistance, and electrical insulation, but also LED emission. It is desirable that the light reflectivity is excellent so that can be used effectively.
- the conventionally used white solder resist composition has a problem that the resin is oxidized and yellowed due to light and heat generated from the LED, and the reflectance decreases with time.
- An object of the present invention is to provide a thermosetting resin composition and a printed wiring board that can prevent discoloration due to light or heat generation and prevent a decrease in reflectance over time.
- thermosetting resin composition capable of preventing the above problem can be provided, and the present invention has been conceived.
- thermosetting resin composition of the present invention contains (A) an epoxy compound having no aromatic ring, (B) a rutile type titanium oxide, (C) a carboxyl group-containing resin, and (D) an organic solvent.
- the inventors used a white compound composed of two liquids, a main agent and a curing agent, when an epoxy compound that is sparingly soluble in an organic solvent such as TEPIC-S manufactured by Nissan Chemical Co., Ltd. is used as the epoxy compound. Recognized the problem that it is difficult to liquefy the thermosetting resin composition.
- the inventors have intensively studied the composition of the composition that facilitates the two-part composition, and as a result, the epoxy compound (A) having no aromatic ring is liquid at room temperature or soluble in an organic solvent. It has been found preferable to use an epoxy compound.
- the resin composition of the present invention it is possible to prevent discoloration due to light or heat generation and to prevent a decrease in reflectance over time.
- the white thermosetting resin composition can be easily liquefied (main agent and curing agent).
- thermosetting resin composition according to the present invention includes an epoxy compound (A) having no aromatic ring, a rutile type titanium oxide (B), a carboxyl group-containing resin (C) and an organic solvent (D).
- epoxy compound (A) having no aromatic ring an epoxy compound that is liquid at room temperature or soluble in an organic solvent is preferable.
- a copolymer resin obtained from a compound having an unsaturated double bond and a compound having an oxirane ring and an ethylenically unsaturated group in one molecule it is preferable to use a copolymer resin obtained from a compound having an unsaturated double bond and a compound having an oxirane ring and an ethylenically unsaturated group in one molecule.
- (meth) acrylate is a term that collectively refers to acrylate and methacrylate, and the same applies to other similar expressions.
- the compound having an oxirane ring and an ethylenically unsaturated group in one molecule it is particularly preferable to use a compound produced from an aliphatic monomer.
- a compound produced from an aliphatic monomer include glycidyl (meth) acrylate, ⁇ -methylglycidyl (meta ) Acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylbutyl (meth) acrylate, 3,4-epoxycyclohexylmethylamino acrylate, 3 , 4-epoxycyclohexylmethyl (meth) acrylate and the like.
- These compounds having an oxirane ring and an ethylenically unsaturated group in one molecule may be used alone or in admixture of two or more.
- the copolymerized epoxy compound (A) having no aromatic ring preferably has an epoxy equivalent in the range of 50 to 1,000 g / mol. More preferably, 100 to 800 g / mol is suitable. When the epoxy equivalent is less than 50 g / mol, crosslinking is insufficient and as a result, the adhesion and pencil hardness are lowered. When it exceeds 1,000 g / mol, the crosslinking density is lowered and sufficient curing cannot be performed, and there are problems such as poor water resistance and electrical properties of the cured coating.
- the weight average molecular weight of the epoxy compound (A) having no aromatic ring is preferably in the range of 3,000 to 100,000. More preferably, 5,000 to 30,000 is appropriate. When the weight average molecular weight is less than 3,000, light resistance and heat resistance tend to be remarkably inferior. On the other hand, if the weight average molecular weight exceeds 100,000, the leveling property and defoaming property during printing are remarkably lowered.
- the amount of the epoxy compound (A) having no aromatic ring is preferably 5 to 100 parts by mass, more preferably 5 to 60 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (C). .
- the compounding amount of the epoxy compound (A) exceeds 100 parts by mass, the ratio of the epoxy compound (A) increases, resulting in excessive crosslinking, and as a result, the coating film is likely to be discolored.
- the amount is less than 5 parts by mass, sufficient curing is not performed, and as a result, adhesion, pencil hardness, and moisture resistance are remarkably impaired, and a practical coating film cannot be obtained.
- the epoxy group of the epoxy compound having no aromatic ring and the carboxyl group of the carboxyl group-containing resin react by ring-opening polymerization.
- rutile type titanium oxide B
- Common titanium oxide includes anatase type and rutile type. Since anatase type titanium oxide has photocatalytic activity, it may cause discoloration of the resin in the solder resist composition.
- rutile-type titanium oxide absorbs near the boundary between the ultraviolet region and the visible light region as compared to anatase-type titanium oxide, and is inferior in terms of whiteness and reflectivity of the entire visible light region, but photoactive Therefore, a stable solder resist film can be obtained.
- the blending amount of such rutile type titanium oxide is preferably 50 to 450 parts by mass, more preferably 60 to 350 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. If the blending amount exceeds 450 parts by mass, the adhesion and leveling properties during printing deteriorate, which is not preferable. On the other hand, when the blending amount is less than 50 parts by mass, the hiding power is small and a high reflectance solder resist cannot be obtained.
- Carboxyl group-containing resin As the carboxyl group-containing resin (C), a photosensitive carboxyl group-containing resin having one or more photosensitive unsaturated double bonds in itself, and a carboxyl group-containing resin having no photosensitive unsaturated double bond Any of the resins can be used and is not limited to a specific one.
- examples of the carboxyl group-containing resin (C) include a copolymer resin obtained by copolymerization of an unsaturated carboxylic acid and a compound having an unsaturated double bond.
- Examples of the unsaturated carboxylic acid constituting such a copolymer resin include acrylic acid, methacrylic acid, and a modified unsaturated monocarboxylic acid having a chain extended between the unsaturated group and the carboxylic acid, such as ⁇ -carboxyethyl (meth).
- ⁇ -carboxyethyl (meth) such as 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, unsaturated monocarboxylic acid having ester bond by lactone modification, modified unsaturated monocarboxylic acid having ether bond, maleic acid, etc.
- those containing two or more carboxyl groups in the molecule may be used alone or in combination of two or more.
- Examples of the compound having an unsaturated double bond include styrene, chlorostyrene, ⁇ -methylstyrene; methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, amyl, 2-ethylhexyl as a substituent.
- a carboxyl group-containing resin having no aromatic ring can be preferably used. As a result, the prevention of discoloration due to light or heat generation becomes more reliable.
- Such a carboxyl group-containing resin (C) preferably has an acid value in the range of 30 to 200 mgKOH / g. More preferably, 50 to 100 mgKOH / g is appropriate. When the acid value is less than 30 mgKOH / g, the crosslinking is insufficient and as a result, the adhesion and pencil hardness are lowered. If it exceeds 200 mgKOH / g, there are problems such as poor water resistance and poor water resistance and electrical properties of the cured coating.
- the weight average molecular weight of the carboxyl group-containing resin (A) is preferably in the range of 1,000 to 100,000. More preferably, 5,000 to 50,000 is appropriate. If the weight average molecular weight is less than 1000, light resistance and heat resistance tend to be extremely inferior. On the other hand, if the weight average molecular weight exceeds 100,000, the leveling property and defoaming property during printing are remarkably lowered.
- organic solvent (D) used in the present invention is used to form a coating film by making the solder resist composition easy to apply and drying it after applying it to a substrate or the like.
- organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetate and esterified products of the above glycol ethers Esters
- the organic solvent can be used alone or as a mixture of two or more.
- the blending amount of the organic solvent is preferably 20 to 300 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
- antioxidant In the present invention, even when the cured product of the solder resist is exposed to a high temperature for a long period of time, an antioxidant is preferably used in order to prevent a decrease in reflectance and coloring of the cured product.
- Such antioxidants include n-octadecyl-3- (3′5′-di-t-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3′-methyl-5 ′ -T-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3- (3'5'-di-t-butyl-4'-hydroxyphenyl) -propionate, 1,6-hexanediol-bis- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate), 1,4-butanediol-bis- (3- (3,5-di-tert-butyl-4-hydroxy
- antioxidants for hindered phenol compounds include Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS -7, Nocrack DAH (all of which are manufactured by Ouchi Shinsei Chemical Co., Ltd.); MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK AO-616, MARK AO-635, MARK AO-658, MARK AO-15, MARK AO-18, MARK 328, MARK AO-37 (all manufactured by ADEKA Corporation); Irganox 245, Irganox 259, Irganox 565, Irganox 1010, Irga Knox 10
- the blending amount of the antioxidant is preferably 0.4 to 25 parts by mass, more preferably 0.8 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
- the blending amount of the antioxidant is less than 0.4 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin, the effect of preventing discoloration due to thermal degradation of the solder resist is small.
- the compounding quantity of antioxidant exceeds 25 mass parts with respect to 100 mass parts of carboxyl group-containing resin, hardening inhibition generate
- a curing agent and / or a curing catalyst can be further added to the white thermosetting resin composition of the present invention.
- the curing agent examples include polyfunctional phenolic compounds, acid anhydrides thereof, aliphatic or aromatic primary or secondary amines, polyamide resins, and polymercapto compounds.
- polyfunctional phenol compounds and acid anhydrides thereof are preferably used from the viewpoints of workability and insulation.
- the polyfunctional phenol compound may be a compound having two or more phenolic hydroxyl groups in one molecule, and known and conventional ones can be used. Specific examples include phenol novolac resins, cresol novolac resins, bisphenol A, allylated bisphenol A, bisphenol F, bisphenol A novolac resins, vinylphenol copolymer resins, and the like. Is preferable because it has a high effect on increasing heat resistance. Such a polyfunctional phenol compound also undergoes an addition reaction with the epoxy compound in the presence of an appropriate curing catalyst.
- the amount of these curing agents to be blended is usually a quantitative ratio, and is preferably 1 to 200 parts by weight, more preferably 10 to 100 parts by weight per 100 parts by weight of the epoxy compound.
- This curing catalyst is a compound that can be a curing catalyst in the reaction between the epoxy compound and the curing agent, or a compound that becomes a polymerization catalyst when no curing agent is used.
- a tertiary amine, a tertiary amine salt, a quaternary Examples thereof include onium salts, tertiary phosphines, crown ether complexes, and phosphonium ylides, and any of these can be used alone or in combination of two or more.
- imidazoles such as trade names 2E4MZ, C11Z, C17Z, 2PZ, AZINE compounds of imidazoles such as trade names 2MZ-A, 2E4MZ-A, trade names 2MZ-OK, 2PZ-OK.
- Isocyanurate of imidazole such as imidazole hydroxymethyl compounds such as trade names 2PHZ and 2P4MHZ (all trade names are manufactured by Shikoku Kasei Kogyo Co., Ltd.), dicyandiamide and derivatives thereof, melamine and derivatives thereof, diaminomaleonitrile and derivatives thereof, Amines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, bis (hexamethylene) triamine, triethanolamine, diaminodiphenylmethane, organic acid dihydrazide, 1,8-diazabicyclo [5,4,0] undecene-7 Trade name DBU, manufactured by San Apro), 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (trade name ATU, manufactured by Ajinomoto Co.), or And organic phosphine compounds such as triphenylphosphine, tricyclohe
- the amount of these curing catalysts to be blended is a normal quantitative ratio, preferably 0.05 to 10 parts by weight, more preferably 0.1 to 3 parts per 100 parts by weight of the epoxy compound having no aromatic ring. Part by mass is appropriate.
- the white thermosetting resin composition of the present invention may further comprise a known and commonly used thickener such as finely divided silica, organic bentonite, montmorillonite, silicone-based, fluorine-based, polymer-based antifoaming agent and / or Alternatively, known and commonly used additives such as leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, and the like can be blended. Further, a colorant can be blended within a range that does not impair the white color of the thermosetting resin composition of the present invention. In particular, phthalocyanine functions and is effective as an anti-settling agent and bluing.
- a known and commonly used thickener such as finely divided silica, organic bentonite, montmorillonite, silicone-based, fluorine-based, polymer-based antifoaming agent and / or Alternatively, known and commonly used additives such as leveling agents, imidazole-based, thiazole-based,
- the white thermosetting resin composition of the present invention is adjusted to a viscosity suitable for the coating method with the organic solvent, and is coated on the substrate by a method such as a screen printing method. After coating, for example, a cured coating film can be obtained by heating to a temperature of 140 ° C. to 180 ° C. and thermosetting.
- the cured coating film of the white thermosetting resin composition according to the present invention is not only suitably used as a solder resist layer in a printed wiring board, but also a component requiring high reflectivity, such as a light emitting element such as an EL or LED. It can be used in a wide range as a reflector.
- Synthesis Example 1 of a carboxyl group-containing resin having no aromatic ring In a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy 2-ethylhexanoate (Nippon Yushi) as a polymerization initiator 21.4 g of trade name; Perbutyl O) manufactured by Co., Ltd. was added and heated to 90 ° C.
- Synthesis example 2 of carboxyl group-containing resin having no aromatic ring In a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy 2-ethylhexanoate (Nippon Yushi) as a polymerization initiator 21.4 g of trade name; Perbutyl O) manufactured by Co., Ltd. was added and heated to 90 ° C.
- Synthesis example 3 of epoxy resin compound soluble in organic solvent among epoxy copolymer compounds having no aromatic ring 3 In a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy 2-ethylhexanoate (Nippon Yushi) as a polymerization initiator 21.4 g of trade name; Perbutyl O) manufactured by Co., Ltd. was added and heated to 90 ° C.
- Test board preparation The solder resist compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were screen printed on an FR-4 copper-clad laminate having a size of 100 mm ⁇ 150 mm and a thickness of 1.6 mm. Using a 100-mesh polyester (made by Bias) plate so that the film thickness is 25 ⁇ m, a pattern is printed with a solid (entire substrate surface) and cured in a hot-air circulating drying oven at 150 ° C. for 30 minutes. Test specimens for testing were prepared.
- the reflectance (Y value) is a value obtained by measuring the Y value of the XYZ color system with a spectrocolorimeter, and the larger the value, the higher the reflectance.
- ⁇ E * ab represents a hue, and a color difference formula between two samples defined by ⁇ L * , ⁇ a * , ⁇ b * , which is a difference between L * , a * , b * in the L * a * b * color system ( It was calculated using the following formula.
- ⁇ E * ab [( ⁇ L * ) 2 + ( ⁇ a * ) 2 + ( ⁇ b * ) 2 ] 1/2 .
- the visual evaluation criteria are: ⁇ : no discoloration, ⁇ : no discoloration, but slight discoloration compared to the initial one, ⁇ : clear discoloration, ⁇ X: A severe discoloration is observed.
- thermosetting resin composition of the present invention was a good result with little change in reflectance Y value in the heat resistance test and light resistance test, and little discoloration in visual evaluation.
- the solder resist composition using the epoxy copolymer compound having no aromatic ring shown in Example 1 showed a particularly small change in the Y value.
- the solder resist formed using the solder resist composition of the present invention has little discoloration due to light and heating over a long period of time, and is excellent in high reflectance.
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Abstract
Description
芳香環を有さないエポキシ化合物(A)としては、常温で液状、もしくは有機溶剤に可溶なエポキシ化合物が好ましい。
本発明では、白色顔料として、ルチル型酸化チタン(B)を用いる。一般的な酸化チタンにはアナターゼ型とルチル型がある。アナターゼ型酸化チタンは、光触媒活性を有するために、ソルダーレジスト組成物中の樹脂の変色を引き起こすことがある。これに対し、ルチル型酸化チタンは、アナターゼ型酸化チタンと比較して紫外線領域と可視光領域の境界付近に吸収があり、白色度と可視光領域全体の反射率の点では劣るものの、光活性を殆ど有さないために、安定したソルダーレジスト膜を得ることができる。
カルボキシル基含有樹脂(C)としては、それ自体に感光性の不飽和二重結合を1個以上有する感光性のカルボキシル基含有樹脂、および感光性の不飽和二重結合を有さないカルボキシル基含有樹脂のいずれも使用可能であり、特定のものに限定されるものではない。
本発明で使用される有機溶剤(D)は、ソルダーレジスト組成物を塗布しやすい状態にし、これを基材等に塗布後乾燥させて塗膜を形成するために用いられる。このような有機溶剤としては、メチルエチルケトン、シクロヘキサノンなどのケトン類;トルエン、キシレン、テトラメチルベンゼンなどの芳香族炭化水素類;メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジプロプレングリコールモノエチルエーテル、トリエチレングリコールモノエチルエーテルなどのグリコールエーテル類;酢酸エチル、酢酸ブチル、セロソルブアセテート、ジエチレングリコールモノエチルエーテルアセテート及び上記グリコールエーテル類のエステル化物などのエステル類;エタノール、プロパノール、エチレングリコール、プロピレングリコールなどのアルコール類;オクタン、デカンなどの脂肪族炭化水素類;石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサなどの石油系溶剤等を挙げることができる。
本発明では、ソルダーレジストの硬化物が長期間に渡り高温にさらされた場合でも、当該硬化物の反射率の低下や着色を防止するため、酸化防止剤が好適に使用される。このような酸化防止剤としては、n-オクタデシル-3-(3’5’-ジ-t-ブチル-4’-ヒドロキシフェニル)-プロピオネート、n-オクタデシル-3-(3’-メチル-5’-t-ブチル-4’-ヒドロキシフェニル)-プロピオネート、n-テトラデシル-3-(3’5’-ジ-t-ブチル-4’-ヒドロキシフェニル)-プロピオネート、1,6-ヘキサンジオール-ビス-(3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)-プロピオネート)、1,4-ブタンジオール-ビス-(3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)-プロピオネート)、トリエチレングリコール-ビス-(3-(3-t-ブチル-5-メチル-4-ヒドロキシフェニル)-プロピオネート)、テトラキス-(メチレン-3-(3’、5’-ジ-t-ブチル-4’-ヒドロキシフェニル)プロピオネートメタン、3,9-ビス(2-(3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ)-1,1-ジメチルエチル)2,4,8,10-テトラオキサスピロ(5,5)ウンデカン、N,N‘-ビス-3-(3’5’-ジ-t-ブチル-4-ヒドロキシフェノール)プリピオニルヘキサメチレンジアミン、N,N’-テトラメチレンビス-3-(3’-メチル-5’-t-ブチル-4-ヒドロキシフェノール)プロピオニルジアミン、N,N’-ビス-(3-(3,5-ジ-t-ブチル-4-ヒドロキシフェノール)プロピオニル)ヒドラジン、N-サリチロイル-N’-サリチリデンヒドラジン、3-(N-サリチロイル)アミノ-1,2,4-トリアゾール、N,N’-ビス(2-(3-(3,5-ジ-ブチル-4-ヒドロキシフェニル)プロピオニルオキシ)エチル)オキシアミド等のヒンダードフェノール化合物、ジドデシル-3,3’-チオジプロピオネート、ジテトラデシル-3,3’-チオジプロピオネート、ジオクタデシル-3,3’-チオジプロピオネート、ジトリデシル-3,3’-チオジプロピオネート、ペンタエリスリチルテトラキス(3-ドデシルチオプロピオネート)、ペンタエリスリチルテトラキス(3-テトタデシルチオプロピオネート)、ペンタエリスリチルテトラキス(3-トリデシルチオプロピオネート)、ジラウリル-3,3-チオジプロピオネート、ジミリスチル-3,3-チオジプロピオネート、ジステアリル-3,3-チオジプロピオネート、ペンタエリスリチルテトラキス(3-ラウリルチオジプロピオネート、2-メルカプトベンゾイミダゾール、ラウリルステアリルチオジプロピオネート、2-メルカプトメチルベンツイミダゾールの亜鉛塩、2-メルカプトベンツイミダゾールの亜鉛塩、2-メルカプトメチルベンツイミダゾール、ジブチルチオカルバミン酸亜鉛等の硫黄系酸化防止剤、トリフェニルホスファイト、トリス(メチルフェニル)ホスファイト、トリイソオクチルホスファイト、トリデシルホスファイト、トリス(2-エチルヘキシル)ホスファイト、トリス(ノニルフェニル)ホスファイト、トリス(オクチルフェニル)ホスファイト、トリス[デシルポリ(オキシエチレン)ホスファイト、トリス(シクロヘキシルフェニル)ホスファイト、トリシクロヘキシルホスファイト、トリ(デシル)チオホスファイト、トリイソデシルチオホスファイト、フェニル・ビス(2-エチルヘキシル)ホスファイト、フェニル・ジイソデシルホスファイト、テトラデシルポリ(オキシエチレン)・ビス(エチルフェニル)ホスファト、フェニル・ジシクロヘキシルホスファイト、フェニル・ジイソオクチルホスファイト、フェニル・ジ(トリデシル)ホスファイト、ジフェニル・シクロヘキシルホスファイト、ジフェニル・イソオクチルホスファイト、ジフェニル・2-エチルヘキシルホスファイト、ジフェニル・イソデシルホスファイト、ジフェニル・シクロヘキシルフェニルホスファイト、ジフェニル・(トリデシル)チオホスファイト等のリン系酸化防止剤、フェニルナフチルアミン、4,4’-ジメトキシジフェニルアミン、4,4’-ビス(α,α-ジメチルベンジル)ジフェニルアミン、ジ-tert-ブチルジフェニルアミン、N,N’-ジ(オクチルフェニル)アミン、4-イソプロポキシジフェニルアミン、N,N’-ジ(2-ナフチル)-p-フェニレンジアミン等の芳香族アミン系酸化防止剤等がある。これらは1種以上を選び、組み合わせても使用できる。中でもヒンダードフェノール化合物が反射率の低下と着色防止の効果が高いため望ましい。ヒンダードフェノール化合物の酸化防止剤の商品名としては、ノクラック200、ノクラックM-17、ノクラックSP、ノクラックSP-N、ノクラックNS-5、ノクラックNS-6、ノクラックNS-30、ノクラック300、ノクラックNS-7、ノクラックDAH(以上いずれも大内新興化学工業(株)製);MARK AO-30、MARK AO-40、MARK AO-50、MARK AO-60、MARK AO-616、MARK AO-635、MARK AO-658、MARK AO-15、MARK AO-18、MARK 328、MARK AO-37(以上いずれも(株)ADEKA製);イルガノックス245、イルガノックス259、イルガノックス565、イルガノックス1010、イルガノックス1035、イルガノックス1076、イルガノックス1081、イルガノックス1098、イルガノックス1222、イルガノックス1330、イルガノックス1425WL(以上いずれもチバ・ジャパン(株)製)があげられる。
この硬化触媒は、エポキシ化合物と上記硬化剤との反応において硬化触媒となり得る化合物、または硬化剤を使用しない場合に重合触媒となる化合物であり、例えば、三級アミン、三級アミン塩、四級オニウム塩、三級ホスフィン、クラウンエーテル錯体、及びホスホニウムイリドなどが挙げられ、これらの中から任意に、単独で又は2種類以上を組み合わせて用いることができる。
芳香環を有さないカルボキシル基含有樹脂の合成例1
攪拌機、温度計、還流冷却器、滴下ロートおよび窒素導入管を備えた2リットルセパラブルフラスコに、溶媒としてジエチレングリコールジメチルエーテル900g、および重合開始剤としてt-ブチルパーオキシ2-エチルヘキサノエート(日本油脂(株)製、商品名;パーブチルO)21.4gを加えて90℃に加熱した。加熱後、ここに、メタクリル酸86g、メタクリル酸メチル849g、を、重合開始剤であるビス(4-t-ブチルシクロヘキシル)パーオキシジカーボネート(日本油脂(株)製、商品名;パーロイルTCP、)21.4gと共に3時間かけて滴下して加え、さらに6時間熟成することにより、固形分の酸価が60.0mgKOH/g、重量平均分子量が15,000の、芳香環を有さないカルボキシル基含有樹脂を51.0質量%(不揮発分)含む溶液を得た。なお、反応は窒素雰囲気下で行った。以下、この反応溶液をA-1ワニスと呼ぶ。
攪拌機、温度計、還流冷却器、滴下ロートおよび窒素導入管を備えた2リットルセパラブルフラスコに、溶媒としてジエチレングリコールジメチルエーテル900g、および重合開始剤としてt-ブチルパーオキシ2-エチルヘキサノエート(日本油脂(株)製、商品名;パーブチルO)21.4gを加えて90℃に加熱した。加熱後、ここに、メタクリル酸309.9g、メタクリル酸メチル116.4g、およびラクトン変性2-ヒドロキシエチルメタクリレート(ダイセル化学工業(株)製、商品名;プラクセルFM1)109.8gを、重合開始剤であるビス(4-t-ブチルシクロヘキシル)パーオキシジカーボネート(日本油脂(株)製、商品名;パーロイルTCP、)21.4gと共に3時間かけて滴下して加え、さらに6時間熟成することにより、カルボキシル基含有共重合樹脂を得た。なお、反応は、窒素雰囲気下で行った。
攪拌機、温度計、還流冷却器、滴下ロートおよび窒素導入管を備えた2リットルセパラブルフラスコに、溶媒としてジエチレングリコールジメチルエーテル900g、および重合開始剤としてt-ブチルパーオキシ2-エチルヘキサノエート(日本油脂(株)製、商品名;パーブチルO)21.4gを加えて90℃に加熱した。加熱後、ここに、メタクリル酸メチル778.6g、グリシジルメタクリレート241.1gを、重合開始剤であるビス(4-t-ブチルシクロヘキシル)パーオキシジカーボネート(日本油脂(株)製、商品名;パーロイルTCP、)21.4gと共に3時間かけて滴下して加え、さらに6時間熟成することにより、分子量 15000、固形分のエポキシ当量が600g/molの芳香環を有さないエポキシ基含有共重有樹脂を52.0質量%(不揮発分)含む溶液を得た。なお、反応は窒素雰囲気下で行った。以下この反応溶液をワニスBと呼ぶ。
備考
A-2ワニス:ジョンクリル67(スチレンアクリル共重合樹脂(BASF JAPAN Ltd)とカルビトールアセテートの56:46(質量比)混合ワニス(芳香環を有さないカルボキシル基含有樹脂)
硬化触媒1;メラミン
硬化触媒2;ジシアンジアミド
酸化チタン;R820 (石原産業社製ルチル型酸化チタン)
TEPIC-S;(日産化学社製)
828;ビスフェノール型エポキシ樹脂(ジャパンエポキシレジン社製)
酸化防止剤:イルガノックス1010(チバ・ジャパン社製)
溶剤:カルビトールアセテート
消泡剤(シリコーンオイル):KS-66(信越シリコーン製)
各ソルダーレジスト組成物を用いて形成されるソルダーレジストの諸性質を調べるために、以下のようにして試験し、評価を行った。
実施例1~4および、比較例1、2のソルダーレジスト組成物を、100mm×150mmの大きさで1.6mmの厚さのFR-4銅張り積層板にスクリーン印刷法にて、膜厚25μmとなるように100メッシュポリエステル(バイアス製)の版を使用してベタ(基板全面)でパターンを印刷し、150℃で30分間に渡って熱風循環式乾燥炉にて硬化させ、特性試験用の試験片を作製した。
得られた試験片を紫外可視光赤外分光光度計(日本分光株式会社製)で反射率を測定し、これを初期値とした。これら試験片をリフロー炉(ピーク温度255℃)に3回通し、その後の各試験片について初期値と同様の条件にて反射率を測定し、各試験片の劣化状態を評価した。また、目視でも当該各試験片を評価した。
得られた試験片を紫外可視光赤外分光光度計(日本分光株式会社製)で反射率を測定し、これを初期値とした。これら試験片をUVコンベアー炉(出力120w/cm、メタルハライドランプ、コールドミラー使用)で、120J/cm2の光を照射し、加速劣化させ再度、初期値と同様に反射率を測定した。また目視でも当該各試験片を評価した。
表2において、反射率(Y値)とはXYZ表色系のY値を分光測色計で測定した値であり、値が大きいほど反射率は高い事を示す。ΔE* abは色相を表し、L*a*b*表色系におけるL*、a*、b*の差であるΔL*、Δa*、Δb*によって定義される二つの試料間の色差式(次式で示す。)を用いて算出した。ΔE* ab=[(ΔL*)2+(Δa*)2+(Δb*)2]1/2。
Claims (5)
- (A)芳香環を有さないエポキシ化合物、(B)ルチル型酸化チタン、(C)カルボキシル基含有樹脂、(D)有機溶剤を含むことを特徴とする熱硬化樹脂組成物。
- 前記芳香環を有さないエポキシ化合物(A)は、常温で液状、もしくは有機溶剤に可溶なエポキシ化合物であることを特徴とする請求項1に記載の熱硬化性樹脂組成物。
- 前記カルボキシル基含有樹脂(C)が、芳香環を有さないことを特徴とする請求項1に記載の熱硬化樹脂組成物。
- 更に、ヒンダードフェノール系化合物を含むことを特徴とする請求項1に記載の熱硬化樹脂組成物。
- 請求項1に記載の熱硬化樹脂組成物を用いて形成した硬化物を有することを特徴とするプリント配線板。
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JP5542915B2 (ja) | 2014-07-09 |
KR20120132534A (ko) | 2012-12-05 |
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