JP6977434B2 - Thermosetting Insulating Resin Composition, Sheet Thermosetting Insulating Resin Composition, Coverlay, and Sheet Thermosetting Insulating Resin Composition with Removable Film - Google Patents

Description

The present invention relates to a thermosetting insulating resin composition containing a surface-treated flame retardant, a sheet-shaped thermosetting insulating resin composition, a coverlay, and a sheet-shaped thermosetting insulating resin composition with a peelable film. Regarding.

In recent years, the development of the electronics field has been remarkable, and in particular, electronic devices have become smaller, lighter, and higher in density, and electronic materials such as printed wiring boards are increasingly required to be thinner, multi-layered, and higher in definition. It is supposed to be done. Even in the case of a thick rigid substrate typified by a conventional glass epoxy substrate or the like, high electrical insulation (hereinafter referred to as insulation) has been required in order to accommodate a narrow space.
However, recent electronic materials such as printed wiring boards and flat cables represented by flexible printed wiring boards (hereinafter referred to as FPCs) can accommodate much narrower spaces than thick rigid boards. Therefore, a higher level of insulation is also required.

Further, due to recent environmental problems, there is a demand for a non-halogen flame retardant material having good flame retardancy without using a halogen flame retardant.
For example, Patent Document 1 discloses that it has (A) a carboxyl group-containing resin, (B) titanium oxide, and (C) a phosphorus compound.

WO2011 / 105277

Patent Document 1 describes that a flame-retardant film can be provided by photo-curing or thermosetting a resin composition for a polyester base material containing a carboxyl group-containing resin, titanium oxide, and a phosphorus compound.
However, it is considered that the above resin composition may have a reduced insulating property under high temperature and high humidity due to impurities derived from the flame retardant.

Improvement of insulation can be expected by increasing the thickness of the insulating layer. However, in the case of FPCs, flat cables, etc., which are required to accommodate narrower spaces, it is difficult to achieve both flame retardancy and insulation. Therefore, the present invention is a thermosetting insulating resin composition for forming an insulating layer suitably used for FPCs, flat cables, etc., and has a thermosetting insulating property capable of achieving both flame retardancy and high insulating properties. It is an object of the present invention to provide a resin composition.

In order to solve the above-mentioned problems, the present inventors have made diligent studies, and as a result, by using a flame retardant obtained by surface-treating the surface of a solid flame retardant with an inorganic oxide such as silica, flame retardant and insulating properties are used. The following inventions [1] to [9] have been completed.

[1] A surface-treated flame retardant (A) in which an inorganic oxide adheres to at least a part of the surface of a solid flame retardant at 25 ° C., a thermosetting resin (B), and the thermosetting resin (B). ) The thermosetting insulating resin composition containing the curing agent (C).

[2] The thermosetting insulating resin composition according to the above [1], wherein 0.01 to 10 parts by mass of an inorganic oxide is attached to 100 parts by mass of a solid flame retardant at 25 ° C.

[3] The thermosetting insulating resin composition according to the above [1] or [2], wherein a silane coupling agent is further adhered to the surface of the surface-treated flame retardant (A).

[4] The thermosetting insulation according to any one of the above [1] to [3], which contains 0.1 to 100 parts by mass of the surface treatment flame retardant (A) with respect to 100 parts by mass of the thermosetting resin (B). Sex resin composition.

[5] The thermosetting insulating resin composition according to any one of the above [1] to [4], wherein the flame retardant solid at 25 ° C. is a phosphinate or a phosphonate.

[6] The thermosetting resin (B) has at least one functional group selected from the group consisting of a carboxyl group, an anhydride group of a carboxyl group, an amino group, and a hydroxyl group, as described above [1] to [5]. The thermosetting insulating resin composition according to any one.

[7] The thermosetting insulating resin composition according to any one of [1] to [6] above, which is in the form of a sheet.

[8] A coverlay in which the sheet-shaped thermosetting insulating resin composition according to the above [7] is arranged on one surface of a heat-resistant resin film.

[9] A sheet-shaped thermosetting insulating resin composition with a peelable film, wherein both sides of the sheet-shaped thermosetting insulating resin composition according to the above [7] are covered with a peelable film.

Thermosetting insulation that can achieve both flame retardancy and high insulation required for FPCs, flat cables, etc. by using a flame retardant whose surface is treated with an inorganic oxide such as silica on the surface of the solid flame retardant. It has become possible to provide a sex resin composition.

A schematic diagram is shown to explain the insulation evaluation method in the present invention.

<Surface treatment flame retardant (A)>
The flame retardant to be surface-treated in the present invention is not particularly limited except that it is solid at 25 ° C., and examples of the shape include powder granules and the like.
In the present invention, a solid at 25 ° C. means a solid having a melting point of 25 ° C. or higher. However, it may include a decomposition reaction as well as melting at the melting point.

For example, (poly) phosphoric acid such as melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium phosphate, ammonium polyphosphate, carbamate phosphate, carbamate polyphosphate, etc. Salt-based compounds, organic phosphoric acid ester compounds, phosphazene compounds, phosphonic acid compounds, aluminum diethylphosphinate, aluminum methylethylphosphinate, aluminum diphenylphosphinate, aluminum ethylbutylphosphinate, aluminum methylbutylphosphinate, aluminum polyethylenephosphinate, etc. Phosphoric acid flame retardant such as phosphoric acid compound, phosphin oxide compound, phosphoran compound, phosphoramide compound;
Nitrogen flame retardants such as ammonium carbonate and melamine cyanurate;
Examples thereof include inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide and calcium hydroxide.

As a flame retardant, it is desirable to use a non-halogen flame retardant such as a phosphorus flame retardant or a nitrogen flame retardant in consideration of the environmental impact, which has been widely discussed in recent years. It is preferable to use a phosphine compound, melamine polyphosphate, ammonium polyphosphate, melamine cyanurate, a hydroxide compound and the like, and among the phosphine compounds, phosphinate is particularly preferable.
Further, in terms of reducing the dielectric constant and the dielectric loss tangent, it is preferable to use a phosphine compound, which is excellent not only in the balance between flame retardancy and insulating property but also in the balance between dielectric property, adhesiveness, flexibility and heat resistance. It becomes possible to obtain a cured product.
In the present invention, these flame retardants can be used alone or in combination of two or more.

The average particle size of these flame retardants is preferably 0.1 to 25 μm. When a flame retardant having an average particle size close to 0.1 μm is used, the reforming effect of the flame retardant can be easily obtained, and the dispersibility and the stability of the dispersion liquid can be easily improved. Further, when a flame retardant having an average particle size close to 25 μm is used, the mechanical properties of the cured product are likely to be improved.
The average particle size referred to in the present invention indicates the particle size when D95 includes a volume integrated value of 95% in the particle size distribution.

The surface-treated flame retardant (A) used in the present invention has an inorganic oxide adhered to at least a part of the surface of the solid flame retardant at 25 ° C.
Although not particularly specified as the inorganic oxide to be adhered, silica, alumina, titania, zirconia and the like are preferably used.

The amount of the inorganic oxide to be attached is preferably 0.01 to 10 parts by mass, more preferably 0.1 part by mass to 10 parts by mass, based on 100 parts by mass of the solid flame retardant at 25 ° C. More preferably, it is 0.1 part by mass to 5 parts by mass. Insulation can be improved by using 0.01 parts by mass or more. Further, when the content is 10 parts by mass or less, the flame retardancy is excellent.

The method for adhering the inorganic oxide to at least a part of the surface of the solid flame retardant at 25 ° C. is not particularly limited, but a spray method, a sol-gel method, or the like is used. For example, the raw material of the inorganic oxide is sprayed on the flame retardant which is the target of the surface treatment, or the raw material of the inorganic oxide and the flame retardant which is the target of the surface treatment are mixed to form a slurry, and then the raw material of the inorganic oxide is prepared. By hydrolyzing or firing the flame retardant, an inorganic oxide can be attached to at least a part of the surface of the flame retardant. The slurry can also be obtained by mixing a raw material of a molten inorganic oxide and a flame retardant to be surface-treated, or is a raw material of an inorganic oxide and a target of surface treatment in a so-called organic solvent. It can also be obtained by dispersing with a flame retardant.

In the present invention, a surface-treated flame retardant (A) having an inorganic oxide adhered to at least a part of the surface of a solid flame retardant at 25 ° C. is further attached with a silane coupling agent. Is preferable. Further, by using the one to which the silane coupling agent is attached, the hydrophobicity of the flame retardant surface can be improved, and the insulation performance can be further improved.

The above-mentioned silane coupling agent is not particularly limited, and for example, vinylmethoxysilane, vinylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycid. Xipropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxy Silane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl)- 2-Aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, 3-isoxapropyltriethoxysilane, 3-phenylaminopropyltrimethoxy In addition to silane, 1,2-ethanediamine, N- {3- (trimethoxysilyl) propyl}-, N- {(ethenylphenyl) methyl} derivative / hydrochloride, vinyltriacetoxysilane, allyltrimethoxysilane, A silane coupling agent in which the functional group is protected by an alkoxy group, a sulfide / polysulfide-based silane coupling agent, a polymer-type alkoxy oligomer type, a polyfunctional group type silane coupling agent, or the like can be used.

The amount of the silane coupling agent to be attached is preferably 0,005 to 5 parts by mass, more preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the solid flame retardant at 25 ° C. preferable. When the amount of the silane coupling agent to be attached is 0.005 part by mass or more, the insulating property is improved. Further, the flame retardancy is excellent when the amount of adhesion is 5 parts by mass or less.

The method for further adhering the silane coupling agent to the surface of the surface treatment flame retardant (A) is not particularly limited, but a dry method or a wet method capable of high-precision treatment is preferably used. In this wet method, a silane coupling agent is added to a dispersion liquid in which a surface-treated flame retardant to which an inorganic oxide is attached is dispersed, a silane coupling agent is bonded to the surface of the surface-treated flame retardant, and then the dispersion medium is removed. It is a method of drying.

<Thermosetting resin (B)>
The thermosetting resin (B) used in the present invention preferably has two or more thermosetting functional groups such as a carboxyl group, an anhydride group thereof, an amino group, and a hydroxyl group in one molecule, but is particularly limited. It's not a thing. Such resins include, for example, polyurethane resin, polyester resin, acrylic resin, polyamide resin, polyimide resin, polyether resin, cyanate resin, phenol resin, styrene-based elastomer which is a block polymer of styrene and olefin, polyolefin resin, and phenoxy resin. , Fluorine resin and the like can be used. Further, an epoxy resin having an epoxy group can be used as the thermosetting resin (B), and a curing agent (C) having an amino group or an anhydride group of a carboxyl group with respect to the epoxy resin can also be used.
The thermosetting resin (B) excludes those having an active energy ray-curable functional group.

The thermosetting insulating resin composition of the present invention preferably contains 0.1 to 100 parts by mass of the surface-treated flame retardant (A) with respect to 100 parts by mass of the thermosetting resin (B), preferably 5 to 80 parts. It is more preferable to contain by mass. When the content of the surface-treated flame retardant (A) is 0.1 part by mass or more, the flame retardancy is excellent. Further, when the content is 80 parts by mass or less, a cured coating film having excellent insulating properties can be obtained.

<Curing agent (C)>
The curing agent (C) used in the present invention may be any as long as it reacts with the reactive functional groups of the thermosetting resin (B), and it is preferable that one molecule of the curing agent has two or more reactive groups. It is not particularly limited. For example, any agent such as an amine curing agent, an anhydride curing agent, an epoxy curing agent, and an isocyanate curing agent can be used.

The thermosetting insulating resin composition of the present invention preferably contains 0.01 to 30 parts by mass of the curing agent (C) with respect to 100 parts by mass of the thermosetting resin (B), preferably 0.1 to 10 parts. It is more preferable to contain it in a quantity portion. From the viewpoint of the pot life of the coating liquid, the content of the curing agent is preferably 0.01 part by mass or more, and from the viewpoint of the crosslink density, it is preferably 30 parts by mass or less.

The thermosetting insulating resin composition of the present invention can be obtained by adding a surface-treated flame retardant (A) and a curing agent (C) to a thermosetting resin (B).
For example, a method of adding a surface-treated flame retardant (A) and a curing agent (C) to a thermosetting resin (B) and dispersing the surface-treated flame retardant (A) using a three-roll or the like, a surface-treated flame retardant ( Examples thereof include a method of preparing a dispersion liquid containing A) and adding it to a mixture of a thermosetting resin (B) and a curing agent (C). Further, in order to disperse the surface-treated flame retardant (A) satisfactorily and to stabilize the dispersed state, a dispersant, a thickener, etc. are used as long as they do not affect the performance of the thermosetting insulating resin composition. It can also be used. Alternatively, the surface-treated flame retardant (A) is added to a part or all of the thermosetting resin (B), the surface-treated flame retardant (A) is well dispersed, and then the remaining thermosetting resin (B) is used. A curing agent (C) can also be added.

The thermosetting insulating resin composition of the present invention contains a volatile liquid medium such as a so-called organic solvent in addition to the surface-treated flame retardant (A) and the curing agent (C) in the thermosetting resin (B). , Can be used as a liquid thermosetting insulating resin composition.
A liquid thermosetting insulating resin composition is applied so as to cover the conductive circuit surface provided on a heat-resistant film such as polyimide, the volatile liquid medium is volatilized, and then a heated oven is used. The thermosetting insulating resin composition can be cured with a heat press or the like, and the conductive circuit surface can be covered with an insulating film.

<Sheet-shaped thermosetting insulating resin composition>
A liquid thermosetting insulating resin composition can be applied to a peelable film to volatilize the volatile liquid medium to obtain a sheet-shaped thermosetting insulating resin composition. Another releaseable film is laminated on the other surface of the formed sheet-shaped thermosetting insulating resin composition, and both sides of the sheet-shaped thermosetting insulating resin composition are covered with the releaseable film. It is also possible to obtain a sheet-like thermosetting insulating resin composition with a peelable film.
These sheet-shaped thermosetting insulating resin compositions are laminated and heated so as to cover the conductive circuit surface provided on the heat-resistant resin film such as polyimide, thereby curing the thermosetting insulating resin composition. The conductive circuit surface can be covered with the cured insulating film.
Examples of the peelable sheet include those obtained by peeling a polyester film.

<Coverlay>
A liquid thermosetting insulating resin composition is applied to a peelable film, the volatile liquid medium is volatilized to obtain a sheet-shaped thermosetting insulating resin composition, and then a sheet-shaped thermosetting resin composition is obtained. The other surface of the heat-insulating resin composition can be covered with a heat-resistant resin film such as polyimide represented by Capton 50EN to form a coverlay with a peelable film.
Alternatively, after applying a liquid thermosetting insulating resin composition to a heat-resistant resin film such as polyimide and volatilizing the volatile liquid medium to obtain a sheet-shaped thermosetting insulating resin composition. It is also possible to cover the other surface of the sheet-shaped thermosetting insulating resin composition with a peelable film to form a coverlay with the peelable film.
Then, the peelable film is peeled off from the coverlay with the peelable film, and a sheet-shaped thermosetting insulating resin composition is layered so as to cover the conductive circuit surface provided on the heat-resistant resin film such as polyimide. The thermosetting insulating resin composition is cured by heating. The cured product of the thermosetting insulating resin composition can be used as an adhesive layer to cover the conductive circuit surface with a heat-resistant resin film.
Examples of the peelable sheet include the same ones as described above.

Hereinafter, the present invention will be described in more detail by way of examples, but the following examples do not limit the scope of rights of the present invention in any way. In the examples, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

(Synthesis Example 1) Synthesis of Surface Treatment Flame Retardant (A1) and Adjustment of Dispersion Obtained in 800 ml of an ethanol solution (concentration: 0.4%) of tetraethyl orthosilicate (hereinafter, also referred to as TEOS) by the method described below. Add 10 g of aluminum phosphinate 1 having a D95 particle size of 5 μm _{, adjust the pH to 12 with concentrated NH 3} water, stir for 3 hours, filter, and wash with ethanol to remove silica on the surface of aluminum phosphinate 1. An attached surface-treated flame retardant (A1) was obtained.
The amount of silica adhering to the surface was determined by ICP emission spectroscopic analysis described later and found to be 0.01 part by mass with respect to 1: 100 parts by mass of aluminum phosphinate.

<Adjustment of dispersion of surface-treated flame retardant>
DISPERBYK-2155 was added as a dispersant to 100 parts by mass of the surface-treated flame retardant (A1) so as to be 15 parts by mass, and the solid content concentration was 35% by mass with a MEK solvent. Then, the mixture was shaken with Scandex for 1 hour to prepare a dispersion of the surface-treated flame retardant (A1).

(Synthesis Examples 2 to 7)
In the same manner as in Synthesis Example 1 except that the amount of aluminum phosphinate 1 added to the ethanol solution of TEOS was changed, the amount of silica adhering to the surface was 0.1 with respect to 100 parts by mass of aluminum phosphinate 1. 0.5, 1, 5, 10, 50 parts by mass of the surface-treated flame retardants (A2) to (A7), and a dispersion having a solid content of 35% by mass were prepared.

(Synthesis Examples 8 to 13)
10 parts by mass of Z-6610 manufactured by Toray Dow Corning Co., Ltd., which is a silane coupling agent, and 10 parts by mass of ethanol while stirring 100 parts by mass of the surface treatment flame retardant (A1) in a mixer and stirring in a nitrogen atmosphere. Was sprayed and heated and stirred at 150 ° C. for 2 hours to remove the solvent and cooled. In this way, a surface-treated flame retardant (A8) in which a silane coupling agent is further adhered to the surface of the surface-treated flame retardant (A1) is obtained, and a dispersion having a solid content of 35% by mass is obtained in the same manner as in Synthesis Example 1. It was adjusted.
The dispersions of (A9) to (A13) were prepared in the same manner except that the amount of the silane coupling agent used for spraying was changed.
The amount of the silane coupling agent in the surface-treated flame retardants (A8) to (A13) was determined by the method described later, and the aluminum phosphinate 1 in the surface-treated flame retardant (A1) was 100. The amount of the silane coupling agent was 0.01, 0.1, 0.2, 0.5, 2.0, 7.0 parts by mass with respect to the mass part.

(Synthesis Examples 14-18)
Except for the use of aluminum phosphinate 2 with a D95 of 10 μm, aluminum phosphinate 3 with a D95 of 20 μm, red phosphorus, magnesium phosphinate hexahydrate, and melamine cyanurate with a D95 of 10 μm instead of aluminum phosphinate 1. Surface-treated flame retardants (A14) to (A18) having 0.5 parts by mass of silica adhering to the surface and each dispersion were obtained in the same manner as in Synthesis Example 3.

(Synthesis Example 19)
50 g of aluminum phosphinate 1 (D95 particle diameter 5 μm) was dispersed in 950 g of pure water, this flame retardant slurry was placed in a reactor with a reflux base, and the pH of the dispersion was adjusted to 11 with a 1 wt% NaOH aqueous solution. Then, the mixture was heated at 95 ° C. for 30 minutes with stirring to obtain a basic slurry of the flame retardant.
Next, _{1250 g of an aqueous solution of sodium aluminate (Na 2} O / Al ₂ O ₃ = molar ratio 1/2) having a concentration of 0.5% by weight as _{Al 2} O ₃ was added at a rate of 5 g / min to the basic slurry of the flame retardant. To obtain a dispersion of aluminum phosphinate 1 having an alumina surface treatment layer.
A cation exchange resin is added to the dispersion and ion exchange is performed until the pH reaches 3, then a slurry containing a flame retardant is separated from the cation exchange resin, dried, and aluminum phosphinate having an alumina surface treatment layer (aluminum phosphinate having an alumina surface treatment layer). A19) was obtained.

(Synthesis Example 20)
Add 200 g of aluminum phosphinic acid 1 (D95 particle diameter 5 μm) _{to a mixed solution of 130 g of isopropyl alcohol and 7.56 g of titanium tetraisopropoxide (Ti [OCH (CH 3} ) ₂ ] ₄ )) and mix at room temperature. Titanium tetraisopropoxide was adsorbed on the surface of aluminum phosphinate 1 with stirring. Next, a mixed aqueous solution of 1.93 g of ion-exchanged water and 1.93 g of isopropyl alcohol is gradually added thereto, and titanium tetraisopropoxide is hydrolyzed, washed, heated, and has a titanium oxide surface-treated layer. Aluminum phosphinate (A20) was obtained.

(Synthesis Example 21)
200 g of aluminum phosphinate 1 (D95 particle diameter 5 μm) was added to 500 g of pure water to obtain an aqueous slurry.
While stirring 500 g of this slurry, the temperature was raised to 40 ° C., and while maintaining this temperature and the pH of the slurry at 7, a 100 g / l zirconium oxychloride aqueous solution corresponding to 1% by mass in terms of _{ZrO 2 with respect to 1 aluminum phosphinate was used.} And 30% sodium hydroxide were added simultaneously over 60 minutes and aged over 30 minutes. This slurry was washed and solid-liquid separated. The obtained solid was heated and calcined at 900 ° C. for 1 hour to obtain aluminum phosphinate (A21) having a zirconium oxide surface treatment layer.

<Quantification of silica surface treatment by ICP emission spectroscopic analysis>
Weigh 0.25 g of surface-treated flame retardant, add 7 ml of nitric acid, and heat continuously at 150 ° C for 2 minutes, 180 ° C for 2 minutes, and 210 ° C for 10 minutes using a microwave-type wet decomposition apparatus. Then, after decomposition treatment with nitric acid, 50 ml was constant-dissolved in distilled water, and ICP measurement (device name: ICP emission spectroscopic analyzer SPECTRO ARCOS manufactured by AMETEK, Inc.) was performed at room temperature.

<Measurement method of D95 particle size>
D95 indicates the particle size when the volume integrated value of 95% is included in the particle size distribution of the flame retardant. The particle size of the flame retardant was measured using Microtrac MT3000EX (manufactured by Nikkiso Co., Ltd.). A measurement sample was prepared by dispersing 0.5 g of a flame retardant while stirring a 1% aqueous solution of sodium dodecylbenzenesulfonate. The measurement was carried out by inputting the refractive index of water and the refractive index of the flame retardant, and adjusting the sample concentration so that the measurement time was 20 seconds and the Signal Level was within the green range.

(Adjustment example) Adjustment of dispersion of untreated flame retardant Instead of the surface-treated flame retardant (A1), aluminum phosphinate 1 having a D95 of 5 μm, aluminum phosphinate 2 having a D95 of 10 μm, and aluminum phosphinate 3 having a D95 of 20 μm Using aluminum hydroxide having a D95 of 0.3 μm, red phosphorus having a D95 of 5 μm, and silica having a D95 of 1 μm, a dispersion of an untreated flame retardant was obtained in the same manner as in the case of Synthesis Example 1.

(Synthesis Example 101) Synthesis of Polyamide Resin 1 431.6 g of Prepole 1009, 109.3 g of 5-HIPA, and terephthalic acid in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, an introduction tube, and a thermometer. 24.9 g, 742.2 g of C36 dimer diamine (priamine 1074: manufactured by Claude Japan Co., Ltd., amine value = 210 mgKOH / g) and 100 g of ion-exchanged water were charged, and the mixture was stirred until the heat generation temperature became constant. When the temperature became stable, the temperature was raised to 110 ° C, and after confirming the outflow of water, the temperature was raised to 120 ° C 30 minutes later, and then the dehydration reaction was continued while raising the temperature by 10 ° C every 30 minutes. .. When the temperature reached 230 ° C., the reaction was continued at the same temperature for 3 hours, and kept under a vacuum of about 2 KPa for 1 hour. Then, the temperature was lowered to obtain a polyamide resin 1. The mass average molecular weight was 23,600, the acid value was 9.53 mgKOH / g, the amine value was 0.20 mgKOH / g, and the phenol value was 25.73 mgKOH / g.

(Synthesis Example 102) Synthesis of polyamide resin 2 202.9 g, 5-HIPA 25,7 g, terephthalic acid, 202.9 g of Pripole 1009, and terephthalic acid in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, an introduction tube, and a thermometer. 35.1 g, 188.4 g of C36 dimer diamine (priamine 1074: manufactured by Claude Japan Co., Ltd., amine value = 210 mgKOH / g) and 100 g of ion-exchanged water were charged, and the mixture was stirred until the heat generation temperature became constant. When the temperature became stable, the temperature was raised to 110 ° C, and after confirming the outflow of water, the temperature was raised to 120 ° C 30 minutes later, and then the dehydration reaction was continued while raising the temperature by 10 ° C every 30 minutes. .. When the temperature reached 230 ° C., the reaction was continued at the same temperature for 3 hours, and kept under a vacuum of about 2 KPa for 1 hour. Then, the temperature was lowered to obtain a polyamide resin 2. The mass average molecular weight was 2,600, the acid value was 87.49 mgKOH / g, the amine value was 0.20 mgKOH / g, and the phenol value was 17.5 mgKOH / g.

(Synthesis Example 103) Synthesis of Polyurethane 1 In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, an introduction tube, and a thermometer, 10.6 g of 1.6-hexanediol and C36 dimerdiol (PRIPL2033: Croder). Made by Japan Co., Ltd., OH value = 207 mgKOH / g) 113.3 g, tolylene isocyanate 44.3 g, and toluene 240 g as a solvent were charged, and the temperature was raised to 60 ° C. with stirring under a nitrogen stream to uniformly dissolve the mixture. Subsequently, 0.016 g of dibutyl tin dilaurate was added to this flask as a catalyst, and the mixture was stirred at 100 ° C. for 3 hours to carry out a urethanization reaction. Next, 40 g of toluene and 17.6 g of trimellitic anhydride were added, and the mixture was stirred at 90 ° C. for 1 hour, then heated to 135 ° C. and reacted for 4 hours. It was cooled to room temperature to obtain a polyurethane resin. The mass average molecular weight was 11,000 and the acid value was 55.3 mgKOH / g.

(Synthesis Example 104) Synthesis of Polyester 1 57.6 g of sebacic acid, 3.2 g of trimesic acid, and cyclohexanedimethanol in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, an introduction tube, and a thermometer. 27.5 g, 1.6-hexanediol 9.7 g, and tetrabutyl titanate 0.012 g were charged, and the mixture was stirred until the exothermic temperature became constant. When the temperature stabilizes, raise the temperature to 110 ° C. After confirming that the temperature has stabilized, raise the temperature to 120 ° C 30 minutes later, and then perform the dehydration reaction while raising the temperature by 10 ° C every 30 minutes. Continued. When the temperature reached 230 ° C., the reaction was continued at the same temperature for 3 hours, and kept under a vacuum of about 2 KPa for 1 hour. Then, the temperature was lowered to obtain a polyester resin. The mass average molecular weight was 32,000 and the acid value was 39.8 mgKOH / g.

(Synthesis Example 105) Synthesis of Acrylic 1 300 g of methylethyl ketone (hereinafter referred to as MEK) is placed in a 4-neck flask equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, an introduction tube, and a thermometer, and nitrogen gas is injected into the container. While heating to 80 ° C., at the same temperature, 30 g of butyl methacrylate, 28 g of methyl methacrylate, a 1: 1 (mass ratio) mixture of lauryl methacrylate and tridecyl methacrylate, 3 g, 12 g of methacrylic acid, 2,2'. -A mixture of 0.8 g of azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropping, the mixture was further reacted at 80 ° C. for 3 hours, then 1.2 parts of 2,2'-azobisisobutyronitrile dissolved in 50 g of MEK was added, and the mixture was reacted at 80 ° C. for 1 hour. An acrylic resin solution was obtained. The mass average molecular weight was 52,000 and the acid value was 78.2 mgKOH / g.

[Example 1]
As a thermosetting resin (B), 100 parts by mass of "M1913" manufactured by Asahi Kasei Co., Ltd., which is a styrene-based elastomer having a carboxylic acid anhydride group, as a curing agent (C), "jER1035" manufactured by Mitsubishi Chemical Co., Ltd. Was added in an amount of 10 parts by mass.
Further, 143 parts (including 50 parts of the surface-treated flame retardant (A1)) of a dispersion (solid content 35% by mass) of the surface-treated flame retardant (A1) was added, and diluted with a MEK solvent so that the solid content concentration became 15%. Then, a liquid thermosetting insulating resin composition was prepared.
This liquid thermosetting insulating resin composition was uniformly applied onto a peel-treated polyester film so that the film thickness after drying was 25 μm, dried, and one side was covered with the peelable film. A sheet-shaped thermosetting insulating resin composition was formed.

[Examples 2 to 7]
The same as in Example 1 except that the dispersions of the surface-treated flame retardants (A2) to (A7) having different amounts of silica adhering to the surface were used instead of the dispersion of the surface-treated flame retardant (A1). Then, liquid and sheet-like heat-curable insulating resin compositions were formed and evaluated in the same manner.

[Examples 8 to 13]
Instead of the dispersion of the surface-treated flame retardant (A1), as shown in Table 2, the dispersions of the surface-treated flame retardants (A8) to (A13) to which the silane coupling agent was further adhered to the surface were used. Liquid and sheet-like thermosetting insulating resin compositions were formed in the same manner as in Example 1 and evaluated in the same manner.

[Examples 14 to 19]
Polyamide resin 1 produced in Synthesis Example 101 as shown in Table 3-1 instead of "M1913" manufactured by Asahi Kasei Co., Ltd., which is a styrene-based elastomer having a carboxylic acid anhydride group as the thermosetting resin (B). ,
Polyamide resin 2, prepared in Synthesis Example 102,
Polyurethane resin 1, prepared in Synthesis Example 103,
Polyester resin 1, produced in Synthesis Example 104,
Acrylic resin 1, prepared in Synthesis Example 105,
In the same manner as in Example 1, liquid and sheet-shaped thermosetting insulating resin compositions were formed and evaluated in the same manner.
Although Example 14 is the same as that of Example 3, it is described as Example 14 according to Table 4 for the sake of clarity.

[Examples 20 to 25]
As the curing agent (C) for the thermosetting resin (B), instead of jER1031S manufactured by Mitsubishi Chemical Co., Ltd., it was changed to Death Module XP2565 manufactured by Sumika Covestro Urethane Co., Ltd. as shown in Table 3-2. Except for the above, liquid and sheet-like thermosetting insulating resin compositions were formed in the same manner as in Examples 14 to 19, and evaluated in the same manner.

[Examples 26 to 35]
The amount of solid content of the surface-treated flame retardant (A1) is 100 parts by mass of "M1913" manufactured by Asahi Kasei Co., Ltd., which is a styrene-based elastomer having a carboxylic acid anhydride group which is a thermosetting resin (B). Liquid and sheet-like thermosetting insulating resin compositions are the same as in Example 1 except that the amount of the dispersion of the surface-treated flame retardant (A1) is changed so as to be the amount shown in Table 4-1. Objects were formed and evaluated in the same manner.

[Examples 36 to 45]
Surface-treated flame retardant (Surface-treated flame retardant (A1) so that the amount of solid content of the surface-treated flame retardant (A1) is the amount shown in Table 4-2 with respect to 1: 100 parts by mass of the polyamide resin which is the thermosetting resin (B). Liquid and sheet-like thermosetting insulating resin compositions were formed in the same manner as in Example 1 except that the amount of the dispersion of A1) was changed, and evaluated in the same manner.

[Examples 46 to 51]
As the surface-treated flame retardant (A), the same as in Example 3 except that the dispersions of the surface-treated flame retardants (A14) to (A18) were used instead of the dispersion of the surface-treated flame retardant (A3). Liquid and sheet-like heat-curable insulating resin compositions were formed and evaluated in the same manner.
Although Example 46 is the same as Example 3, for the sake of clarity, it is shown as Example 46 in accordance with Table 5.

[Examples 52 to 57]
Of the 50 parts by mass of the surface-treated flame retardant (A3) contained in the thermosetting insulating resin composition in Example 3, 15 parts by mass was not adjusted in the adjustment example so as to be replaced with the untreated flame retardant. Liquid and sheet-like thermosetting insulating resin compositions were formed in the same manner as in Example 3 except that the dispersion of the treated flame retardant was used, and evaluated in the same manner.

[Examples 58 to 61]
Liquid and sheet-like thermosetting insulation in the same manner as in Example 3 except that the dispersions of (A19) to (A21) prepared in Synthesis Examples 19 to 21 were used as the surface treatment flame retardant (A). A sex resin composition was formed and evaluated in the same manner.

[Comparative Examples 1 to 7]
In Comparative Examples 1 to 6, 50 parts of each of the following dispersions of the untreated flame retardant obtained in the adjusted example were used instead of the surface-treated flame retardant (A1), except that 50 parts of each was used.
Further, in Comparative Example 7, a dispersion of aluminum phosphinate 1 and a dispersion of silica were used in combination of 25 parts by mass instead of the surface-treated flame retardant (A1).
Liquid and sheet-like photosensitive insulating resin compositions were formed in the same manner as in Example 1 and evaluated in the same manner.
Comparative Example 1: Dispersion of aluminum phosphinate 1 having a D95 of 5 μm Comparative Example 2: Dispersion of aluminum phosphinate 2 having a D95 of 10 μm Comparative Example 3: Dispersion of aluminum phosphinate 3 having a D95 of 20 μm
Comparative Example 4: Dispersion of aluminum hydroxide with D95 of 0.3 μm Comparative Example 5: Dispersion of red phosphorus with D95 of 5 μm Comparative Example 6: Dispersion of silica with D95 of 1 μm Comparative Example 7: Hosphin with D95 of 5 μm A dispersion of aluminum acid 1 and a dispersion of silica having a D95 of 1 μm.

The flame-retardant and electrically insulating properties of the sheet-shaped thermosetting insulating resin composition whose one side was covered with the peelable film obtained in Examples and Comparative Examples were evaluated by the following methods. The results are shown in Tables 1-7.

(1) Flame retardancy (preparation of sample for flame retardancy evaluation)
A polyimide film [manufactured by Toray DuPont Co., Ltd. [Kapton 50EN]] having a thickness of 12.5 μm was prepared as a heat-resistant resin film.
After laminating the heat-resistant resin film at 80 ° C. on the side of the sheet-like thermosetting insulating resin composition whose one side is covered with the peelable film, which is not covered with the peelable film, 160 ° C. The film was heated for 60 minutes and then thermoset.
In the obtained laminate, a heat-resistant resin film, a cured product of a thermosetting insulating resin composition, and a peelable film are laminated in this order.

(Evaluation of flame retardancy)
The obtained laminate was cut into a size of 20 cm × 20 cm, the peelable film was peeled off, and then the heat-resistant resin film was rolled into a cylinder so as to face outward to obtain a test piece for evaluation.
A thin vertical combustion test conforming to the UL94 standard was performed on this test piece, and the result was judged according to the length of combustion according to the following criteria.
A ... Combustion distance ≤ 1 cm
B ... 1 cm <combustion distance ≤ 3 cm
C ... 3 cm <combustion distance ≤ 5 cm
D ・ ・ ・ 5cm <Combustion distance ≤ 7cm
E ・ ・ ・ 7cm <Combustion distance ≤ 10cm
F ・ ・ ・ 10cm <Combustion distance

(2) Electrical insulation (preparation of sample for insulation evaluation)
A printed wiring board having three types of comb-shaped copper circuit patterns (conductor pattern width / space width = 50 μm / 50 μm, 100 μm / 100 μm, 200 μm / 200 μm) formed on a polyimide film was prepared (see FIG. 1 (1)). ).
After laminating the circuit surface of the printed wiring board at 80 ° C. on the side not covered with the peelable film of the sheet-like thermosetting insulating resin composition whose one side is covered with the peelable film, The heat-curable insulating resin composition in the form of a sheet was heat-cured by heating at 160 ° C. for 60 minutes.
In the obtained laminate, the circuit surface of the printed wiring board, the cured product of the photosensitive insulating resin composition, and the peelable film are laminated in this order.

(Evaluation of insulation)
The peelable film was peeled off from the laminate to prepare a test piece for evaluating the insulating property (see FIG. 1 (2)). In the figure, for the sake of explanation, the comb-shaped copper circuit is shown so as to be visible through the cured product of the photosensitive insulating resin composition.
Under two types of atmospheres, a temperature of 60 ° C. and a relative humidity of 85%, and a temperature of 80 ° C. and a relative humidity of 85%, a DC voltage of 50 V was continuously applied to the copper circuit of the test piece for insulation evaluation for 100 hours, respectively. The time (hr) until the leak touch (short) was measured under one atmosphere. The evaluation criteria are as follows.
A ... No leak touch until 100 hours later at any temperature and circuit pattern.
B ... Leak touch occurred within 100 hours under the conditions of a temperature of 85 ° C. and a circuit pattern of 50/50, but no leak touch occurred until after 100 hours under conditions other than the above.
C ... Leak touch occurred within 100 hours under the conditions of a temperature of 85 ° C. and circuit patterns of 50/50 and 100/100, but no leak touch occurred until after 100 hours under conditions other than the above.
D ... Leak touch occurred within 100 hours under the conditions of temperature 85 ° C. and all circuit patterns, but no leak touch occurred until after 100 hours under the conditions of temperature 60 ° C. and all circuit patterns.
E ... Leak touch occurred by 100 hours under the condition of temperature 85 ° C. and all circuit patterns, and leak touch occurred by 100 hours under the condition of circuit pattern 50/50 at temperature 60 ° C. At a temperature of 60 ° C., no leak touch occurred until after 100 hours under at least one of the circuit patterns 100/100 and 200/200.
F ... Leak touch occurred within 100 hours under all conditions.

As shown in Examples 1 to 7 of Table 1, when the amount of adhered silica is increased, the flame retardancy tends to decrease and the insulating property tends to improve.

As shown in Examples 8 to 14 of Table 2, the insulating property is improved by increasing the amount of the attached silane coupling agent, but tends to be deteriorated by increasing the amount of the added silane coupling agent.

As shown in Examples 14 to 25 of Table 3-1 and Table 3-2, the same effect as in Example 3 could be confirmed even in the case of other thermosetting resins and other curing agents.

As shown in Examples 26 to 45 of Tables 4-1 and 4-2, the more the surface-treated flame retardant is added, the more the flame retardancy is improved, but the insulating property tends to be deteriorated.

As shown in Examples 46 to 51 of Table 5, flame retardancy is improved by using a surface-treated flame retardant having a small particle size. This is because a small particle size flame retardant having a large surface area is more advantageous in terms of flame retardancy mechanism.

As shown in Examples 58 to 61 of Table 7, silica is preferable as the inorganic oxide to be adhered to the surface of the flame retardant from the viewpoint of improving the insulating property.

As shown in Comparative Examples 1 to 6 in Table 8, when no surface-treated flame retardant is added, the flame retardancy is significantly deteriorated. Further, as shown in Comparative Example 7, even when silica is simply blended as a dispersion without adhering to the flame retardant in advance, the flame retardancy deteriorates and the insulating property is not so effective.

1: Polyimide film 2: Cathode electrode connection point 2': Cathode electrode connection point 3: Anode electrode comb signal wiring 3': Anode electrode connection point 4: Cured product of photosensitive insulating resin composition

Claims (9)

At least a part of the surface of the phosphinate flame retardants are solid at 2 5 ° C., spraying or surface treatment flame retardant made by adhering inorganic oxide (A) by a sol-gel method, a thermosetting resin (B ) And a thermosetting insulating resin composition containing a curing agent (C) for the thermosetting resin (B).
(However, the thermosetting resin (B) does not have an active energy ray-curable functional group.) The thermosetting insulating resin composition according to claim 1, wherein 0.01 to 10 parts by mass of an inorganic oxide is attached to 100 parts by mass of a solid flame retardant at 25 ° C. The thermosetting insulating resin composition according to claim 1 or 2, which contains 0.1 to 100 parts by mass of the surface-treated flame retardant (A) with respect to 100 parts by mass of the thermosetting resin (B). The invention according to any one of claims 1 to 3 , wherein the thermosetting resin (B) has at least one functional group selected from the group consisting of a carboxyl group, an anhydride group of a carboxyl group, an amino group, and a hydroxyl group. Thermosetting insulating resin composition. The thermosetting insulating resin composition according to any one of claims 1 to 4, wherein a silane coupling agent is further attached to the surface of the surface treatment flame retardant (A). The amount of the silane coupling agent adhering to the surface of the surface-treated flame retardant (A) is 0.01 to 7.0 parts by mass with respect to 100 parts by mass of phosphinate, which is a solid flame retardant at 25 ° C. Item 5. The heat-curable insulating resin composition according to Item 5. The thermosetting insulating resin composition according to any one of claims 1 to 6, which is in the form of a sheet. A coverlay in which the sheet-shaped thermosetting insulating resin composition according to claim 7 is arranged on one surface of a heat-resistant resin film. The sheet-shaped thermosetting insulating resin composition with a peelable film, wherein both sides of the sheet-shaped thermosetting insulating resin composition according to claim 7 are covered with a peelable film.

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