CN111378088A - Thermosetting resin composition, dry film, cured product, and electronic component - Google Patents
Thermosetting resin composition, dry film, cured product, and electronic component Download PDFInfo
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- CN111378088A CN111378088A CN201811637557.0A CN201811637557A CN111378088A CN 111378088 A CN111378088 A CN 111378088A CN 201811637557 A CN201811637557 A CN 201811637557A CN 111378088 A CN111378088 A CN 111378088A
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/54—Polycondensates of aldehydes
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- 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
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- 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
- C08K2003/2241—Titanium dioxide
Abstract
Provided are a thermosetting resin composition, a dry film, a cured product, and an electronic component, wherein the cured product has high reflectance and excellent discoloration resistance, heat resistance, and flexibility. A thermosetting resin composition comprising A) an isocyanate compound and B) a hydroxyl group-containing hydrocarbon resin, wherein the B) hydroxyl group-containing hydrocarbon resin comprises: a hydrocarbon resin having a weight-average molecular weight of 1000 or more, having at least one skeleton selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton, and a biphenol skeleton, and containing a hydroxyl group.
Description
Technical Field
The invention relates to a thermosetting resin composition, a dry film, a cured product and an electronic component.
Background
In recent years, light emitting elements such as LEDs that emit light at low power have been put into practical use as backlights for liquid crystal displays of mobile terminals, personal computers, televisions, and the like, light sources for lighting fixtures, and the like. The use of directly mounting these light emitting elements in a printed circuit board has also increased. In this case, an insulating film formed as a protective film on a printed wiring board is required to have excellent light reflectance, heat resistance, and weather resistance, and to have flexibility for use in a flexible printed wiring board such as polyimide.
Conventionally, in order to obtain a light reflectance, a curable resin composition in which an inorganic filler having a high reflectance such as titanium oxide is blended in a curing system of a carboxyl group-containing resin, a photopolymerizable monomer, a photopolymerization initiator, and an epoxy resin has been proposed (see patent document 1), but there is a problem that flexibility and heat resistance of a cured product thereof are insufficient.
Further, when the light source is exposed to light for a long time, deterioration such as yellowing due to light occurs, and the reflectance may be lowered. Further, in a heating step such as soldering when mounting a light emitting element on a substrate, since the light emitting element is exposed to a high temperature of 250 ℃. In view of the above, there have been proposed a composition of an epoxy resin and imidazole, a composition of an acid anhydride and an epoxy resin, a two-liquid thermosetting resin composition in which a copolymer of styrene-maleic anhydride and a polyfunctional alicyclic epoxy resin are mixed, and a curable resin composition of a polyester resin and an isocyanate compound (see patent documents 2 to 4). However, these compositions have a problem that the flexibility, reflectance and discoloration resistance of the cured product are insufficient.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2010-224171
Patent document 2: japanese patent laid-open No. 2005-36218
Patent document 3: japanese patent laid-open publication No. 2010-229221
Patent document 4: chinese patent laid-open publication No. 108227378
Disclosure of Invention
Problems to be solved by the invention
As described above, conventional curable resin compositions have not obtained a cured film having high reflectance and excellent discoloration resistance, heat resistance, and flexibility. The present invention has been made to solve the above problems, and an object thereof is to provide a thermosetting resin composition which can realize a cured product having high reflectance and excellent discoloration resistance, heat resistance, and flexibility, a dry film, a cured product thereof, and an electronic component using the same.
Means for solving the problems
As a result of intensive studies, the present inventors have succeeded in obtaining a thermosetting resin composition which can realize a cured product having high reflectance and excellent discoloration resistance, heat resistance and flexibility by combining an isocyanate compound and a hydrocarbon resin having a weight-average molecular weight of 1000 or more, at least one skeleton selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton and a biphenol skeleton, and containing a hydroxyl group, and have completed the present invention.
Namely, the present invention is as follows.
[ item 1 ] to
A thermosetting resin composition characterized by containing:
A) an isocyanate compound,
B) A hydrocarbon resin containing a hydroxyl group, a hydroxyl group-containing hydrocarbon resin,
the aforementioned B) hydroxyl group-containing hydrocarbon resin comprises: a hydrocarbon resin having a weight-average molecular weight of 1000 or more, having at least one skeleton selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton, and a biphenol skeleton, and containing a hydroxyl group.
[ item 2 ] A method for producing a semiconductor device
The thermosetting resin composition according to claim 1, wherein the hydrocarbon resin having a weight average molecular weight of 1000 or more and having at least one skeleton selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton and a biphenol skeleton and containing a hydroxyl group is contained in an amount of 40 parts by mass or more per 100 parts by mass of the hydrocarbon resin containing a hydroxyl group of the B).
[ item 3 ] A method for producing a semiconductor device
The thermosetting resin composition according to claim 1 or 2, wherein the hydrocarbon resin having a weight average molecular weight of 1000 or more, having at least one skeleton selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton, and a biphenol skeleton, and containing a hydroxyl group comprises: a hydrocarbon resin having a weight average molecular weight of 10000 or more, having at least one skeleton selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton, and a biphenol skeleton, and containing a hydroxyl group.
[ item 4 ] A
The thermosetting resin composition according to claim 3, wherein the hydrocarbon resin having a weight average molecular weight of 10000 or more, at least one skeleton selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton and a bicresol skeleton, and containing a hydroxyl group is 50 parts by mass or more per 100 parts by mass of the hydrocarbon resin having a weight average molecular weight of 1000 or more, at least one skeleton selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton and a bicresol skeleton, and containing a hydroxyl group.
[ item 5 ] A method for producing a semiconductor device
The thermosetting resin composition according to any one of claims 1 to 4, further comprising C) a white pigment.
[ item 6 ] A composition for treating a tumor
The thermosetting resin composition according to any one of claims 1 to 5, which is used for forming a protective film for electronic components.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a thermosetting resin composition which can realize a cured product having high reflectance and excellent discoloration resistance, heat resistance, and flexibility, a dry film using the same, a cured product, and an electronic component can be provided.
Detailed Description
The present invention is a thermosetting resin composition containing A) an isocyanate compound and B) a hydroxyl group-containing hydrocarbon resin, wherein the B) hydroxyl group-containing hydrocarbon resin contains: a hydrocarbon resin having a weight-average molecular weight of 1000 or more, having at least one skeleton selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton, and a biphenol skeleton, and containing a hydroxyl group.
The respective components of the thermosetting resin composition of the present invention are described below. It should be noted that (meth) acrylate refers to a term collectively referring to acrylate, methacrylate and a mixture thereof, and the same is true for other similar expressions below.
A) Isocyanate compound
The isocyanate compound A) contained in the thermosetting resin composition of the present invention is added as a thermosetting component. The isocyanate compound A) constitutes a curing system together with the hydrocarbon resin containing a hydroxyl group B) described in detail later, and is advantageous for improving flexibility and soldering heat resistance of the cured film.
Examples of the isocyanate compound a) include aromatic isocyanates, aliphatic isocyanates, and alicyclic isocyanates. These isocyanates may be used in the form of polymers such as 2-mer and 3-mer, blocked isocyanates masked with alcohol and/or phenol, and bis-urethane (bisurethane) compounds. Typical examples of the multimer include, but are not limited to, uretdione modified products, biuret modified products, and isocyanurate modified products, which are 2-mers.
Specific examples of the aromatic isocyanate include 4, 4' -diphenylmethane diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, naphthalene-1, 5-diisocyanate, orthophenylenedimethylene diisocyanate, m-xylylene diisocyanate, triphenylmethane triisocyanate, and polymethylenepolyphenyl polyisocyanate.
Specific examples of the aliphatic isocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, and trimethylhexamethylene diisocyanate.
Specific examples of the alicyclic isocyanate include 4, 4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, and bicycloheptane triisocyanate.
These isocyanates may be used in1 kind or in combination of 2 or more kinds. Among them, 2-functional isocyanates are preferably used. Specifically, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and blocked isocyanates, uretdione modifications, and isocyanurate modifications corresponding thereto are more preferably used.
Commercially available products of the isocyanate compound A) include HI-100 manufactured by BASF corporation, TKA-100 manufactured by Asahi Kasei Chemicals, TPA-100, 24A-100, Karenz M0I manufactured by Showa Denko K.K., 7950, 7951, 7960, 7961, 7982, 7991 manufactured by Baxenden K.K.
The amount of the a) isocyanate compound is not particularly limited, but when the amount of the a) isocyanate compound is too low, curing may be insufficient and soldering heat resistance may be poor, and when too high, flexibility of the cured film may be impaired. The amount of the isocyanate compound of A) is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, and even more preferably 10 to 50 parts by mass per 100 parts by mass of the hydroxyl group-containing hydrocarbon resin of B) in order to obtain both flexibility and solder heat resistance of a cured film at a high level.
B) Hydrocarbon resin containing hydroxyl group
As the hydroxyl group-containing hydrocarbon resin B) contained in the thermosetting resin composition of the present invention, any known and conventional hydrocarbon resin, for example, an aromatic hydrocarbon resin, an aliphatic hydrocarbon resin, an alicyclic hydrocarbon resin, a copolymerized hydrocarbon resin, or the like can be used as long as it contains one or more hydroxyl groups in the molecule and the main skeleton is composed of a hydrocarbon.
In the present invention, at least a part of the hydroxyl group-containing hydrocarbon resin B) contains an aromatic hydrocarbon resin having at least one skeleton (hereinafter, also referred to as a specific skeleton) selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton, and a biphenol skeleton. Among these specific skeletons, a bisphenol skeleton is preferable in terms of realizing a cured product having discoloration resistance and soldering heat resistance.
The hydrocarbon resin containing a hydroxyl group of B) is preferably an aromatic hydrocarbon resin having the above-mentioned specific skeleton from the viewpoint of flexibility of the cured film, and further preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a biphenol aldehyde varnish type epoxy resin, a biphenol type epoxy resin, or a phenoxy resin, or a modified product thereof from the viewpoint of improving curability of the composition and flexibility of the cured film.
The amount of the hydroxyl group-containing hydrocarbon resin B) may be 5 to 45 mass%, preferably 8 to 34 mass%, more preferably 12 to 28 mass%, particularly preferably 15 to 24 mass% of the total composition. If the amount is less than the above range, the strength of the coating film is undesirably reduced. On the other hand, if the amount is more than the above range, the viscosity of the composition becomes high, or the coating property and the like become low, which is not preferable.
In the thermosetting resin composition of the present invention, sufficient discoloration resistance and flexibility cannot be obtained if B) the hydroxyl group-containing hydrocarbon resin consists of only (B1) a hydroxyl group-containing hydrocarbon resin having a weight average molecular weight of less than 1000 and the specific skeleton (hereinafter also referred to simply as (B1) hydrocarbon resin) and/or a hydroxyl group-containing hydrocarbon resin having no specific skeleton. Therefore, the above-mentioned B) hydroxyl group-containing hydrocarbon resin contains (B2) a hydrocarbon resin having a weight average molecular weight of 1000 or more, having at least any one skeleton selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton and a biphenol skeleton, and containing a hydroxyl group (hereinafter also simply referred to as (B2) hydrocarbon resin) as an essential component. In contrast, the upper limit of the weight average molecular weight of the hydrocarbon resin (B2) is not particularly limited, and may be 350000 or less, and further 250000 or less, for example.
From the viewpoint of ease of acquisition, the bisphenol skeleton of the (B2) hydrocarbon resin preferably includes a bisphenol a skeleton and a bisphenol F skeleton. EPICLON H-304-40 manufactured by DIC is commercially available as the hydrocarbon resin (B2).
The (B2) hydrocarbon resin is contained in an amount of 40 parts by mass or more, more preferably 60 parts by mass or more, and particularly preferably 80 parts by mass or more per 100 parts by mass of the B) hydroxyl group-containing hydrocarbon resin, in order to obtain a cured product having excellent discoloration resistance and flexibility. The upper limit of the content is not particularly limited, and the above-mentioned B) hydroxyl group-containing hydrocarbon resin may be composed of only the above-mentioned (B2) hydrocarbon resin.
From the viewpoint of obtaining more excellent discoloration resistance and flexibility, the (B2) hydrocarbon resin preferably contains a hydrocarbon resin having a weight average molecular weight of 10000 or more, having at least one skeleton selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton, and a biphenol skeleton, and containing a hydroxyl group. More preferably, the resin composition contains a bisphenol A type epoxy resin and a bisphenol F type epoxy resin having a weight average molecular weight of 10000 or more and containing a hydroxyl group.
The hydrocarbon resin having a weight average molecular weight of 10000 or more, having at least one skeleton selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton, and a biphenol skeleton, and containing a hydroxyl group is preferably contained by 50 parts by mass or more, more preferably 75 parts by mass or more, and particularly preferably 90 parts by mass or more per 100 parts by mass (B2) of the entire hydrocarbon resin. The upper limit of the content thereof is not particularly limited, and the (B2) hydrocarbon resin may be composed of only the hydrocarbon resin having the weight average molecular weight of 10000 or more, having at least any one skeleton selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton and a biphenol skeleton, and containing a hydroxyl group.
(B2) The epoxy equivalent of the epoxy resin used in the hydrocarbon resin is not particularly limited as long as the lower limit of the weight average molecular weight is satisfied, and is, for example, 400 or more, preferably 800 or more, more preferably 2000 or more, and still more preferably 5000 or more.
Other ingredients
The thermosetting resin composition of the present invention may contain a coloring pigment having a high reflectance at an emission wavelength, particularly (C) a white pigment in the case of visible light, when a high reflectance is required, for example, for a mounting substrate of a light-emitting device. As the white pigment (C), for example, zinc oxide, titanium oxide, aluminum oxide, zirconium oxide, and the like are suitably used, and particularly, titanium oxide is preferable because high reflectance can be obtained.
The amount of the white pigment (C) is, for example, 40 to 70 parts by mass, preferably 50 to 60 parts by mass, per 100 parts by mass of the hydroxyl group-containing hydrocarbon resin (B). Even if the amount exceeds 70 parts by mass, the reflectance is not improved, and there is a fear that dispersion becomes difficult. On the other hand, if the amount is less than 40 parts by mass, the effect of improving the reflectance by the white pigment (C) may be insufficient.
As the titanium oxide that can be used in the thermosetting resin composition of the present invention, titanium oxide produced by a sulfuric acid method or a chlorine method, rutile type titanium oxide, anatase type titanium oxide, or titanium oxide subjected to a surface treatment with a hydrated metal oxide or a surface treatment with an organic compound can be used. Titanium oxide is classified into rutile type and anatase type according to the crystal structure. Among them, rutile type titanium oxide is preferable. Anatase titanium oxide is often used because it has a higher whiteness than rutile titanium oxide. However, anatase titanium oxide has photocatalytic activity, and thus may cause discoloration of a resin in a photocurable and thermosetting resin composition. On the other hand, rutile titanium oxide is slightly inferior in whiteness to anatase titanium oxide, but hardly has photoactivity, and thus a stable cured film can be obtained.
As the rutile type titanium oxide, a known rutile type titanium oxide can be used. Specifically, there can be used TR-600, TR-700, TR-750, TR-840, R-550, R-580, R-630, R-820, CR-50, CR-58, CR-60, CR-90, CR-97, KR-270, KR-310, KR-380, etc., all available from Fuji titanium industries, Ltd. Among these rutile-type titanium oxides, titanium oxide having a surface treated with hydrated alumina or aluminum hydroxide is particularly preferably used from the viewpoint of dispersibility in the composition, storage stability, and flame retardancy.
The thermosetting resin composition of the present invention may further contain a thermosetting component other than A) the isocyanate compound. Examples of the other thermosetting component include epoxy resins and/or episulfide resins other than the hydroxyl group-containing hydrocarbon resin of B), amine resins such as melamine resins, melamine derivatives, benzoguanamine resins and benzoguanamine derivatives, known and conventional thermosetting resins such as cyclic carbonate compounds, bismaleimides, oxazine compounds, oxazoline compounds and carbodiimide resins. Examples of the compound include methylol melamine compounds, methylolbenzoguanamine compounds, methylolglycoluril compounds, methylolurea compounds, and the like. Further, the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound and alkoxymethylated urea compound can be obtained by converting the methylol group of each of the methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound into an alkoxymethyl group. The kind of the alkoxymethyl group is not particularly limited, and for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group and the like can be used. Particularly, a melamine derivative having a formalin concentration of 0.2% or less which is friendly to the human body and environment is preferable.
The other thermosetting components may be used alone in1 kind or in combination of 2 or more kinds.
The thermosetting resin composition of the present invention may further contain a thermosetting catalyst when an epoxy resin is contained as the above-mentioned B) hydroxyl group-containing hydrocarbon resin or when an epoxy resin and/or an episulfide resin which is not contained in the above-mentioned B) hydroxyl group-containing hydrocarbon resin is contained as the other thermosetting component. Examples of such a thermosetting catalyst include imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, and 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphine compounds such as triphenylphosphine, and commercially available products include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole compounds), U-CAT (registered trademark) 3503N, U-CAT3502T (all trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATA SA102, and U-CAT5002 (all bicyclic amidine compounds and salts thereof), which are manufactured by Kabushiki Kaisha. They are not particularly limited, and may be used alone or in combination of 2 or more. Further, an s-triazine derivative such as guanamine, methylguanamine, benzoguanamine, melamine, 2, 4-diamino-6-methacryloyloxyethyl-s-triazine, 2-vinyl-2, 4-diamino-s-triazine, 2-vinyl-4, 6-diamino-s-triazine-isocyanuric acid adduct, 2, 4-diamino-6-methacryloyloxyethyl-s-triazine-isocyanuric acid adduct, or the like may be used, and it is preferable to use a compound which also functions as an adhesion imparting agent in combination with the aforementioned heat curing catalyst.
The amount of the thermosetting catalyst to be blended is sufficient in a usual amount ratio, and is, for example, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass, based on100 parts by mass of the hydroxyl group-containing hydrocarbon resin of B).
The aforementioned heat curing catalysts may be used alone in1 kind or in combination in2 or more kinds.
The thermosetting resin composition of the present invention may contain an antioxidant for the purpose of reducing discoloration due to deterioration caused by heat applied to a coating film and/or oxidative deterioration. Examples of the antioxidant include (1) radical scavengers capable of neutralizing generated radicals; and/or (2) a peroxide decomposer which decomposes the generated peroxide into harmless substances without generating new radicals.
Specific examples of the antioxidant which functions as a radical scavenger include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2, 6-di-t-butyl-p-cresol, 2-methylene-bis (4-methyl-6-t-butylphenol), 1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3, 5-tris (3 ', 5' -di-t-butyl-4-hydroxybenzyl) -s-triazine-2, 4, phenol-based compounds such as 6- (1H,3H,5H) trione, quinone-based compounds such as hydroquinone monomethyl ether (methoquinone) and benzoquinone, and amine-based compounds such as bis (2,2,6, 6-tetramethyl-4-piperidyl) -sebacate and phenothiazine.
Examples of the radical scavenger include commercially available products such as Adekastab AO-30, Adekastab AO-330, Adekastab AO-20, Adekastab LA-77, Adekastab LA-57, Adekastab LA-67, Adekastab LA-68, Adekastab LA-87 (trade name, manufactured by Asahi electro-chemical Co., Ltd.), IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN144, TINUVIN 152, TINUVIN292, and TINUVIN 5100 (trade name, manufactured by Ciba Specialty Co., Ltd.).
Specific examples of the antioxidant which functions as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, and sulfur compounds such as pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, and distearyl 3, 3' -thiodipropionate.
Examples of the peroxide decomposer include Adekastab TPP (trade name, manufactured by Asahi Denka Co., Ltd.), Mark AO-412S (trade name, manufactured by Adeka Argus Chemical Co., Ltd.), and SUMILIZER TPS (trade name, manufactured by Sumitomo Chemical Co., Ltd.).
The amount of the antioxidant to be blended is preferably 0.4 to 25 parts by mass, more preferably 0.8 to 15 parts by mass, per 100 parts by mass of the hydroxyl group-containing hydrocarbon resin of B). When the amount is less than 0.4 parts by mass, the effect of preventing discoloration due to deterioration caused by heat applied to the coating film is small, and when the amount exceeds 25 parts by mass, it becomes difficult to obtain heat resistance and storage stability.
The antioxidant may be used singly in1 kind or in combination of 2 or more kinds.
In addition, since the polymer material generally absorbs light and is decomposed/deteriorated, an ultraviolet absorber may be used in addition to the antioxidant in order to take measures against stabilization of ultraviolet rays in the thermosetting resin composition of the present invention.
Examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, and dibenzoylmethane derivatives. Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2' -dihydroxy-4-methoxybenzophenone, and 2, 4-dihydroxybenzophenone. Specific examples of the benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, p-tert-butylphenyl salicylate, 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate, and the like. Specific examples of the benzotriazole derivative include 2- (2 ' -hydroxy-5 ' -tert-butylphenyl) benzotriazole, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, and 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-amylphenyl) benzotriazole. Specific examples of the triazine derivative include hydroxyphenyl triazine, bis (ethylhexyloxyphenol) methoxyphenyl triazine, and the like.
Examples of the ultraviolet absorber include commercially available products such as TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, and TINUVIN 479 (the above are Ciba Specialty Chemicals Co., Ltd., trade name).
The ultraviolet absorber may be used alone or in combination of 1 or more, and is used in combination with the antioxidant to stabilize a molded product obtained from the thermosetting resin composition of the present invention.
The thermosetting resin composition of the present invention can reduce light deterioration by further containing a hindered amine light stabilizer.
Examples of the hindered amine light stabilizer include TINUVIN622LD, TINUVIN 144; CHIMASSORB944LD and CHIMASSORB 119FL (both of Ciba Specialty Chemical Company); MARK LA-57, LA-62, LA-67, LA-63, LA-68 (all of which are manufactured by Adeka Argus Chemical Co., Ltd.); sanol LS-770, LS-765, LS-292, LS-2626, LS-1114, LS-744 (all of which are manufactured by Sankyo Life Co., Ltd.).
The light stabilizer is preferably added in an amount of 0.1 to 10 parts by mass based on100 parts by mass of the hydroxyl group-containing hydrocarbon resin B).
The light stabilizer can be used singly or in combination of 1 or more.
When the thermosetting resin composition of the present invention contains (C) a white pigment such as titanium oxide, the dispersibility and the settleability of the (C) white pigment can be improved by containing a dispersant. Examples thereof include ANTI-TERRA-U, ANTI-TERRA-U100, ANTI-TERRA-204, ANTI-TERRA-205, DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-108, DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-167, DISPERYK-168, DISPERBYK-170, DISPERBYK-183, DISPERYK-174, DISPERBYK-183, DISPERYK-183, DISPERB-183, DISPERYK-183, DISPERB-183, DISPERY, DISPERBYK-2070, DISPERBYK-2096, DISPERBYK-2150, BYKP104, BYK-P104S, BYK-P105, BYK-9076, BYK-9077, BYK-220S (manufactured by BYKJapan K.K.), DISPARON 2150, DISPARON 1210, DISPARON KS-860, DISPARON KS-873N, DISPARON7004, DISPARON 1830, DISPARON 1860, DISPARON 1850, DISPARON DA-400N, DISPARON PW-36, DISPARON DA-50 (manufactured by Nanguo Kabushiki Kaisha), FLOWLEN G-450, WLEN-600, WLEN G-820, FLONG-700, WLEN-44, DOPA-17 (manufactured by FLON 703 K.K.).
In order to effectively achieve the above object, the content of the dispersant is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the (C) white pigment. More preferably 0.5 to 5 parts by mass.
The foregoing dispersants may be used singly in1 kind or in combination in2 or more kinds.
The thermosetting resin composition of the present invention may be incorporated with a photopolymerizable monomer having 2 or more ethylenically unsaturated groups in the molecule to make the composition photocurable. The composition of the present invention thus produced into a photocurable and thermosetting resin composition can be cured by heating after photocuring and patterning by alkali development, thereby forming a cured film having a desired pattern.
The photopolymerizable monomer that can be used in the photocurable and thermosetting resin composition is photocured by irradiation with active energy rays, and the resin composition of the present invention is rendered insoluble in an aqueous alkali solution or contributes to insolubilization of the resin composition of the present invention in an aqueous alkali solution. Examples of such photopolymerizable monomers include diacrylates of glycols such as ethylene glycol, methoxyethylene glycol, polyethylene glycol, and propylene glycol; polyacrylates such as polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and trishydroxyethyl isocyanurate, and ethylene oxide adducts and propylene oxide adducts thereof; polyacrylates such as phenoxy acrylate, bisphenol a diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols; glycidyl ether-based polyacrylates such as glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; and melamine acrylate and/or various methacrylates corresponding to the above acrylates.
Further, there may be mentioned: epoxy acrylate resins obtained by reacting a polyfunctional epoxy resin such as cresol novolak type epoxy resin with acrylic acid; and an epoxy urethane acrylate compound obtained by reacting a hydroxyl group of the epoxy acrylate resin with a hydroxyl acrylate such as pentaerythritol triacrylate and a half-urethane compound of a diisocyanate such as isophorone diisocyanate. The epoxy acrylate resin can improve photocurability without reducing finger-touch dryness.
The amount of the photopolymerizable monomer having 2 or more ethylenically unsaturated groups in the molecule is 5 to 100 parts by mass, and more preferably 1 to 70 parts by mass, based on100 parts by mass of the hydroxyl group-containing hydrocarbon resin of B). When the amount is less than 5 parts by mass, the photo-curability is lowered, and it is difficult to form a pattern by alkali development after irradiation with active energy rays, which is not preferable. On the other hand, when the amount is more than 100 parts by mass, the solubility in an aqueous alkali solution is lowered, and the coating film becomes brittle, which is not preferable.
When the photopolymerizable monomer is blended in the thermosetting composition of the present invention, a photopolymerization initiator may be used together. Such a photopolymerization initiator is not particularly limited as long as it can be used for a curable resin composition.
Examples thereof include aromatic ketones such as benzophenone, N ' -tetraalkyl-4, 4 ' -diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-acetone-1, 4 ' -bis (dimethylamino) benzophenone (mikrolon), 4 ' -bis (diethylamino) benzophenone, 4-methoxy-4 ' -dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-morpholinobenzophenone) -butanone-1, 2-ethylanthraquinone, and mixtures thereof, Aromatic ketones such as phenanthrenequinone, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether, benzoin derivatives such as benzoin methyl benzoin and ethyl benzoin, benzoin derivatives such as benzil dimethyl ketal, 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-bis (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, 2, 4-bis (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2, 4-dimethoxyphenyl) -4, 5-diphenylimidazole dimer, 2,4, 5-triarylimidazole dimer, Acridine derivatives such as 9-phenylacridine and 1, 7-bis (9, 9' -acridinyl) heptane, N-phenylglycine derivatives, coumarin-based compounds, and the like.
These photopolymerizable monomers and photopolymerization initiators may be used alone or in the form of a mixture of 2 or more.
The thermosetting resin composition of the present invention may further contain an organic solvent for use in preparation of the composition and adjustment of viscosity. As the organic solvent, ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like can be cited. More specifically, there are ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha.
Such organic solvents may be used alone or in the form of a mixture of 2 or more.
The thermosetting resin composition of the present invention may further contain, as required, known and conventional additives such as a thickener such as fine powder silica, organobentonite, and montmorillonite, a defoaming agent and/or a leveling agent such as silicone-based, fluorine-based, and polymer-based, a silane coupling agent such as imidazole-based, thiazole-based, and triazole-based, an antioxidant, and a rust preventive.
The thermosetting resin composition of the present invention may be in the form of a dry film comprising a carrier film (support) and a layer formed of the thermosetting resin composition on the carrier film.
In the case of dry coating, the thermosetting resin composition of the present invention is diluted with the organic solvent to adjust the viscosity to an appropriate value, and the diluted thermosetting resin composition is coated on a carrier film in a uniform thickness by a die coater, a knife coater, a lip coater, a bar coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, or the like, and dried at a temperature of 50 to 130 ℃ for 1 to 30 minutes, so that a resin layer as a dry coating film can be produced. The resin layer is not particularly limited, and is preferably selected in the range of 10 to 150 μm, preferably 20 to 60 μm, in terms of the film thickness after drying.
As the carrier film, a plastic film is used, and preferably a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like is used. The thickness of the carrier film is not particularly limited, and is usually suitably selected within the range of 10 to 150 μm.
In this case, after the resin layer is formed on the carrier film, a releasable cover film is preferably further laminated on the surface of the resin layer for the purpose of preventing adhesion of dust to the surface of the resin layer. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used, and when peeling the cover film, the adhesion between the resin layer and the cover film is smaller than the adhesion between the resin layer and the carrier film.
Another embodiment of the present invention provides a cured product obtained from the thermosetting resin composition or the dry film thereof.
The thermosetting resin composition of the present invention is adjusted to a viscosity suitable for a coating method as needed, and is applied to a printed wiring board on which a circuit is formed by a method such as screen printing, curtain coating, spray coating, or roll coating, and an organic solvent contained in the composition is evaporated and dried at a temperature of, for example, 60 to 100 ℃ as needed, thereby forming a non-tacky coating film. Then, in the case of the coating film or the dry film resin layer obtained, for example, formed from a photocurable and thermosetting resin composition, if necessary, exposure is selectively performed by irradiation of active energy rays through a photomask on which a predetermined exposure pattern is formed, and the unexposed portion is developed with a developing solution to form a resist pattern. Further, the cured product is heated to a temperature of 140 to 180 ℃ for thermosetting, for example, to obtain a cured product having high reflectance and excellent discoloration resistance, heat resistance and flexibility as a protective film for electronic parts.
Heating for volatilization drying and thermosetting after coating the thermosetting resin composition of the present invention can be performed using a hot air circulation type drying oven, an IR oven, a hot plate, a convection oven, or the like (a method of bringing hot air in a drying machine into convection contact using a device provided with a heat source of a steam-based air heating system, and a system of blowing the hot air to a support body by a nozzle).
Another embodiment of the present invention provides an electronic component having the cured product. Such electronic components are used for, for example, backlights of liquid crystal displays of portable terminals, personal computers, televisions, and the like, and light emitting elements such as LEDs.
Examples
The present invention will be specifically described below by way of examples and comparative examples, but the present invention is not limited to the following examples. In the following, unless otherwise specified, "parts" and "%" are based on mass.
The thermosetting resin compositions of the respective examples were obtained by mixing the components shown in table 1 at the mixing ratios of the solid components shown in table 1 (mass basis).
[ TABLE 1 ]
Remarking:
1 TPA-100. hexamethylene diisocyanate isocyanurate modified body, NCO content 23.1%, Asahi Kasei Chemicals Co., Ltd
224A-100. hexamethylene diisocyanate, NCO content 23.5%, Asahi Kasei Chemicals K.K
3MH-700 G.4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride, acid anhydride equivalent weight 161-166, and Nippon chemical and physical preparation
4Vylon 200. TOYOBO CO., LTD system
5CELLOXIDE 2021. cndot.3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexanecarboxylate, epoxy equivalent of 128 to 145, Daicel chemical
6850S. bisphenol A type hydrocarbon resin, molecular weight about 380, produced by DIC K.K
74005P. bisphenol F type hydrocarbon resin, molecular weight about 3700, Mitsubishi chemical corporation
81256. bisphenol A type hydrocarbon resin, molecular weight of about 51000, product of Mitsubishi chemical corporation
9H-304-40. bisphenol A type hydrocarbon resin, molecular weight about 24000, produced by DIC corporation
10 CR-97. rutile titanium oxide having an average particle diameter of 0.25 μm, available from Stone Ltd
11 CR-58. rutile titanium oxide, average particle diameter 0.28. mu.m, Property test by Shinyuan Co., Ltd.:
1) reflectivity of light
Each of the compositions of examples and comparative examples was applied to a copper solid substrate by screen printing so that the dry film thickness was 25 to 30 μm, and then cured by heating at 150 ℃ for 60 minutes. The cured film thus obtained was measured for reflectance at a wavelength of 460nm by a spectrocolorimeter (CM-2600d, manufactured by Konica Minolta Sensing, Inc.).
2) Resistance to discoloration
The substrate obtained from the reflectance was subjected to heat treatment at 200 ℃ for 30 minutes and 60 minutes, and then the change rate Δ E of the substrate before and after the treatment was determined using a color difference meter. The criteria for determination are as follows.
< criterion for judgment of discoloration resistance >
◎, Delta E is 2 or less
○, Delta E is more than 2 and not more than 3
△ Δ E is more than 3 and less than 4
× delta E is more than 4
3) Solder heat resistance
Each of the compositions of the examples and comparative examples was applied to a polyimide film (Kapton 100H, manufactured by Duponts) using an applicator so that the dry film thickness was 25 to 30 μm, and the film was cured by heating at 150 ℃ for × 60min in a hot air circulating furnace to prepare an evaluation substrate, and the obtained evaluation substrate was immersed in a solder bath at 260 ℃ to visually observe the surface state of the coating film.
< judgment reference for welding Heat resistance >
○ even if the dipping was repeated 2 times for 10 seconds, there was no peeling.
△ slight peeling occurred when the immersion was repeated 2 times for 10 seconds.
× peeling occurred due to 1 immersion for 10 seconds.
4) Flexibility (bending test)
The compositions of the examples and comparative examples were applied to a polyimide film (Kapton 100H, manufactured by Duponts) using an applicator, and cured by heating at 150 ℃ for × 60min in a hot air circulating furnace to obtain an evaluation substrate.
The film was repeatedly bent at 180 ° by seaming, and the state of crack generation in the film was observed visually with an optical microscope at a magnification of 200, to evaluate the number of times of crack generation.
< criteria for judgment >
◎ the preparation is administered more than 5 times
○ for 2-4 times
× the dosage is less than 1 time
The results of the above-described evaluation tests are shown in table 2.
[ TABLE 2 ]
As is apparent from table 2, the evaluation of the reflectance, discoloration resistance, solder heat resistance, and flexibility of examples 1 to 6 using a) the isocyanate compound (a) in combination with (B2) the hydrocarbon resin having a weight average molecular weight of 1000 or more and a bisphenol skeleton and containing a hydroxyl group all gave excellent results. The evaluation of the reflectance, discoloration resistance, and flexibility of examples 3 to 6 using the (B2) hydrocarbon resin having a weight average molecular weight of 10000 or more gave further excellent results.
On the other hand, comparative example 1, which used a (B1) hydrocarbon resin having a weight average molecular weight of less than 1000 and did not contain a (B2) hydrocarbon resin, was insufficient in discoloration resistance and poor in weld heat resistance. Comparative example 2 using a conventional curing system based on a combination of a polyester resin and an isocyanate compound was poor in discoloration resistance and solder heat resistance. Comparative example 3, which used a conventional curing system based on a combination of an acid anhydride and an alicyclic epoxy resin, had insufficient discoloration resistance and poor solder heat resistance and flexibility.
These results demonstrate that the thermosetting resin composition of the present invention can form a cured product having high reflectance and excellent discoloration resistance, heat resistance, and flexibility. The thermosetting resin composition of the present invention, a dry film using the same, and a cured product thereof are suitably used for, for example, a backlight of a liquid crystal display such as a mobile terminal, a personal computer, and a television, and an electronic component in a light emitting element such as an LED.
Claims (6)
1. A thermosetting resin composition characterized by containing:
A) an isocyanate compound,
B) A hydrocarbon resin containing a hydroxyl group, a hydroxyl group-containing hydrocarbon resin,
the B) hydroxyl group-containing hydrocarbon resin comprises: a hydrocarbon resin having a weight-average molecular weight of 1000 or more, having at least one skeleton selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton, and a biphenol skeleton, and containing a hydroxyl group.
2. The thermosetting resin composition according to claim 1, wherein the hydrocarbon resin having a weight average molecular weight of 1000 or more and having at least one skeleton selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton and a biphenol skeleton and containing a hydroxyl group is contained in an amount of 40 parts by mass or more per 100 parts by mass of the B) hydrocarbon resin containing a hydroxyl group.
3. The thermosetting resin composition according to claim 1 or 2, wherein the hydrocarbon resin having a weight average molecular weight of 1000 or more, having at least any one skeleton selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton, and a biphenol skeleton, and containing a hydroxyl group comprises: a hydrocarbon resin having a weight average molecular weight of 10000 or more, having at least one skeleton selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton, and a biphenol skeleton, and containing a hydroxyl group.
4. The thermosetting resin composition according to claim 3, wherein the hydrocarbon resin having a weight average molecular weight of 10000 or more, at least one skeleton selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton, and a bicresol skeleton, and containing a hydroxyl group is 50 parts by mass or more per 100 parts by mass of the hydrocarbon resin having a weight average molecular weight of 1000 or more, at least one skeleton selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton, and a bicresol skeleton, and containing a hydroxyl group.
5. The thermosetting resin composition according to any one of claims 1 to 4, further comprising C) a white pigment.
6. The thermosetting resin composition according to any one of claims 1 to 5, which is used for forming a protective film for electronic parts.
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