KR20220019106A - A structure having a substrate composed of a liquid crystal polymer and a cured film of a thermosetting composition formed on the surface of the substrate - Google Patents

Abstract

[Problem] To provide a structure comprising a substrate made of a liquid crystal polymer and a cured film of a thermosetting composition formed on the surface of the substrate, wherein the cured film is prevented from peeling from the substrate and excellent in solder heat resistance.
[Solutions] A structure having a substrate composed of a liquid crystal polymer and a cured film of a thermosetting composition formed on the surface of the substrate, wherein the thermosetting composition comprises (A) a thermosetting component and (B) aluminum oxide particles. It is a structure characterized by

Description

A structure having a substrate composed of a liquid crystal polymer and a cured film of a thermosetting composition formed on the surface of the substrate

The present invention relates to a structure having a substrate composed of a liquid crystal polymer and a cured film of a thermosetting composition formed on the surface of the substrate.

Conventionally, conductor patterns have been formed on flat substrates such as copper-clad laminates, glass substrates, ceramic substrates, and wafer plates using paper phenol, paper epoxy, etc., but liquid crystal polymer (LCP), polyether ether ketone (PEEK), polyphenylene alcohol Since high-temperature thermoplastic super engineering plastics such as feed (PPS) have heat resistance that can withstand heating in the reflow process during mounting of parts on printed wiring boards, in recent years, three-dimensional molded products of super engineering plastics have been used as circuit-forming substrates. It is being considered for use as In addition, the three-dimensional circuit molded part in which the circuit is formed on the base material of the three-dimensional molded object and the part is mounted is called MID (Mold Interconnect Device).

Patent Document 1 discloses an invention relating to a substrate for MID in which a three-dimensional molded product of a thermoplastic resin having heat resistance such as a liquid crystal polymer (LCP) or polyether ether ketone (PEEK) is coated with a thermosetting resin such as an epoxy resin.

According to the MID using the board|substrate of patent document 1, since a circuit can be formed in the surface of a three-dimensional molded object of a compact and complex shape, the thing which conforms to the trend of light, thin, short and small electronic components can be manufactured.

Japanese Patent Laid-Open No. 2018-115355

As mentioned above, liquid crystal polymer (LCP), polyether ether ketone (PEEK), polyphenylene sulfide (PPS), etc. are known as super engineering plastics. Among these, LCP is especially, mechanical strength, electrical property, and chemical-resistance. Expectations are high because of this excellence.

However, when a cured film of the curable resin composition is formed on the surface of a substrate made of LCP (hereinafter also referred to as an LCP substrate), there is a problem that the cured film is peeled off together with the surface layer of the LCP substrate.

In view of the above problems, an object of the present invention is a structure having a substrate composed of a liquid crystal polymer and a cured film of a thermosetting composition formed on the surface of the substrate, wherein the cured film and the LCP substrate have excellent adhesion and solder heat resistance. is to provide

The present inventors have conducted intensive studies to achieve the above object. As a result, the cause of the peeling is that the LCP substrate has a low coefficient of thermal expansion (CTE), and the CTE difference from the curable resin composition used in the past is large, but the surface of the LCP substrate is It was thought that it was because it was easy to fibrillate, these causes were discovered by mix|blending aluminum oxide particle with curable resin composition, and it came to complete this invention.

That is, the above object of the present invention is,

A structure comprising: a substrate composed of a liquid crystal polymer; and a cured film of a thermosetting composition formed on the surface of the substrate;

The thermosetting composition,

(A) a thermosetting component;

(B) aluminum oxide particles

It has been found to be achieved by a structure characterized in that it comprises a.

In addition, the liquid crystal polymer has the following formulas (a) and/or formulas (b)

It is preferable that it is a liquid crystal polyester resin containing the repeating unit represented by, or a wholly aromatic liquid crystal polyester resin comprised of the said repeating unit.

In addition, the substrate composed of the liquid crystal polymer is ASTM D648 (1.82 MPa) (standard number of ASTM standard, which is a standard formulated and issued by ASTM International (formerly American Society for Testing and Materials)) It is preferable that load deflection temperature (DTUL) is 140 degreeC or more and 350 degrees C or less.

ADVANTAGE OF THE INVENTION According to this invention, when a thermosetting composition is apply|coated on the base material (LCP base material) comprised by liquid crystal polymer, the problem of peeling of the obtained cured film can be eliminated.

<Thermosetting composition>

The thermosetting composition used in the structure of the present invention is a thermosetting composition applied on the surface of the LCP substrate,

(A) a thermosetting component;

(B) aluminum oxide particles

includes

The LCP base material is excellent in that it can withstand the heat when a conductor pattern is formed and then parts are mounted by reflow soldering or flow soldering, and also excellent in moldability, electrical properties, and chemical resistance. In addition, the melting point (melting temperature measured according to JIS K 7121 using a differential scanning calorimeter) of LCP is generally 270 to 370°C.

The liquid crystal polymer used for the LCP substrate used in the present invention is a polyester or polyesteramide that forms an anisotropic melt phase, and is particularly limited as long as it is called a thermotropic liquid crystal polyester or a thermotropic liquid crystal polyesteramide in the technical field. there is no The LCP base material may further add an inorganic filler as needed, or may use it together with a glass cloth. Examples of the inorganic filler include fibrous inorganic fillers such as glass fibers and carbon fibers, short-fibrous fillers (whiskers such as silicon carbide, silicon nitride, and zinc oxide), and plate-shaped inorganic fillers such as talc and mica.

When the fibrous inorganic filler is added, regarding the shape thereof, the fiber diameter is preferably in the range of 6 to 15 µm, and the aspect ratio is preferably in the range of 5 to 60. When a plate-shaped inorganic filler is used, the plate-shaped inorganic filler has an average length of 1 to 80 µm, preferably 1 to 50 µm, and an average aspect ratio (length/thickness) of 2 to 60, preferably 10 to 40. ) is preferred.

A fibrous inorganic filler, a short fibrous filler (whisker), and a plate-shaped inorganic filler may be used individually, respectively, and may be used in combination of 2 or more type. Moreover, a powdery or needle-like inorganic filler may be added. Moreover, as a coloring agent, carbon black etc. may be added to the LCP base material.

The properties of the anisotropic melt phase can be confirmed by a conventional polarization inspection method using orthogonal polarizers. Specifically, confirmation of the anisotropic molten phase can be performed by observing the sample mounted on the Leitz hot stage at 40 times magnification using a Leitz polarization microscope in nitrogen atmosphere. The liquid crystal polymer used for the LCP substrate of the present invention is optically anisotropic, ie, transmits light when inspected with orthogonal polarizers. If the sample is optically anisotropic, even in a stationary state, polarized light is transmitted.

Examples of the polymerizable monomer constituting the liquid crystal polymer include aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic aminocarboxylic acid, aromatic hydroxyamine, aromatic diamine, aliphatic diol and aliphatic dicarbon. can be heard The liquid crystal polymer may be a homopolymer of one type of these polymerizable monomers or a copolymer of two or more types of polymerizable monomers. .

The polymerizable monomer constituting the liquid crystal polymer may be an oligomer formed by bonding one or more of the compounds exemplified above.

As a liquid crystal polymer, since it is excellent in fluidity|liquidity and mechanical properties, the liquid-crystalline polyester resin containing the repeating unit represented by Formula (a) and/or Formula (b), or the wholly aromatic liquid-crystalline polyester resin comprised by the co-coating unit can be used appropriately.

The thermosetting composition used in the present invention is particularly preferably used when the LCP substrate is a substrate on which a conductor pattern is formed by injection molding. In addition, when a three-dimensional molded product of an injection-molded LCP substrate is used as a substrate for forming a conductor pattern, the LCP substrate is required to maintain rigidity even when heated at a high temperature.

Specifically, the LCP substrate has a deflection temperature under load (DTUL) based on ASTM D648 (1.82 MPa) of 140°C or more and 350°C or less, preferably 180°C or more and 310°C or less, and particularly preferably 200°C or more and 290°C or less. is below.

When the above-mentioned bending temperature under load of the LCP base material is 140°C or more and 350°C or less, it does not deform even during heating of brazing, and molding processing is also facilitated.

An example of the measurement of the specific load deflection temperature (DTUL) is shown below.

Using an injection molding machine (manufactured by Nissei Jushi Kogyo Co., Ltd., UH1000-110), injection molding was performed at a cylinder temperature of +20 to 40°C of crystal melting temperature and a mold temperature of 70°C, and a rectangular test piece (length 127 mm × width 12.7 mm × thickness of 3.2 mm). Based on ASTM D648 using this, the temperature used as a predetermined|prescribed deflection amount (0.254 mm) is measured with 1.82 MPa of load and 2 degreeC/min of temperature increase rate.

As a commercial item of the LCP base material whose load deflection temperature is 140 degreeC or more and 350 degreeC, Vectra (trademark) E841iLDS, Vectra (trademark) E840iLDS (above, Celanese Japan company make), TECACOMP (registered trademark) LCP LDS black 4107 (black4107) (made by Ensinger), RTP 3499-3 X 113393A (made by RTP), etc. are mentioned. Moreover, the said LCP base material whose bending temperature under load is 140 degreeC or more and 350 degrees C or less is marketed also by Ueno Seiyaku.

[(A) thermosetting component]

A thermosetting component is a compound added in order to thermoset the thermosetting composition used by this invention.

As a thermosetting component used for this invention, amine resins, such as a melamine resin and a benzoguanamine resin, a polyisocyanate compound, a block isocyanate compound, a cyclocarbonate compound, a polyfunctional epoxy compound, a polyfunctional oxetane compound, an episulfide resin , a melamine derivative, a benzoguanamine derivative, a bismaleimide, an oxazine compound, an oxazoline compound, a carbodiimide compound, and other known and usual thermosetting resins can be used. Particularly preferable is a thermosetting component having a plurality of cyclic ether groups or cyclic thioether groups (hereinafter, abbreviated as “cyclic (thio)ether groups”) in the molecule.

The thermosetting component having a plurality of cyclic (thio) ether groups in such a molecule is a compound having a plurality of groups of any one or two types of a 3, 4 or 5 membered cyclic ether group or a cyclic thioether group in the molecule, for example, a molecule A compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, that is, an episulfide resin, etc. can

As said polyfunctional epoxy compound, Mitsubishi Chemical Corporation jER828, jER834, jER1001, jER1004, Daicel Chemicals Co., Ltd. EHPE3150, DIC Corporation EPICLON 840, EPICLON 850, EPICLON 1050, EPICLON 2055, the Shin-Nippon Chemical Co., Ltd. make Epotto YD-011, YD-013, YD-127, YD-128, Dow Chemical DER317, DER331, DER661, DER664, Huntsman Japan Araldite 6071, Araldite 6084, Bisphenol-A epoxy resins, such as Araldite GY250, Araldite GY260, and Sumitomo Chemical Co., Ltd. Sumi epoxy ESA-011, ESA-014, ELA-115, ELA-1284 (all are brand names); Mitsubishi Chemical Corporation jERYL903, DIC Corporation EPICLON 152, EPICLON 165, Shin-Nittetsu Chemical Corporation Epotto YDB-400, YDB-500, Dow Chemical Corporation DER542, Huntsman Japan Corporation Araldite 8011 , Sumitomo Chemical Co., Ltd. brominated epoxy resins, such as ESB-400 and ESB-700 (all are brand names); Mitsubishi Chemical Corporation jER152, jER154, Dow Chemical Corporation DEN431, DEN438, DIC Corporation EPICLON N-730, N-770, EPICLON N-865, Shin-Nittetsu Chemical Corporation Epotto YDCN-701, YDCN-704, Huntsman Japan Araldite ECN1235, Araldite ECN1273, Araldite ECN1299, Araldite XPY307, Nippon Kayaku EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000, Sumitomo Chemical Co., Ltd. Sumi Epoxy ESCN-195X, ESCN-220, ECN-235, ECN-299, etc. (all are brand names) novolak-type epoxy resin; Bisphenols such as EPICLON 830 manufactured by DIC, jER807 manufactured by Mitsubishi Chemical Corporation, Epottoto YDF-170, YDF-175, YDF-2004 manufactured by Nippon Chemicals, Araldite XPY306 manufactured by Huntsman Japan (all are brand names) F-type epoxy resin; Hydrogenated bisphenol A epoxy resins, such as Epotto ST-2004, ST-2007, and ST-3000 (brand name) by the Shin-Nippon-Sumikin Chemical company; JER604 manufactured by Mitsubishi Chemical, Epottoto YH-434 manufactured by Nippon Steel Chemicals, Araldite MY720 manufactured by Huntsman Japan, Sumi Epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (all are brand names) Cydylamine type epoxy resin; Hydantoin-type epoxy resins such as Araldite CY-350 (trade name) manufactured by Huntsman Japan; alicyclic epoxy resins such as Celoxide 2021 manufactured by Daicel Chemical Industries, Ltd., and Araldite CY175 and CY179 manufactured by Huntsman Japan (all are brand names); Trihydroxyphenylmethane type epoxy resins, such as YL-933 by Mitsubishi Chemical Corporation, EPPN-501 by Nippon Kayaku, and EPPN-502 (all are brand names); Bixylenol type or biphenol type epoxy resins, such as YL-6056, YX-4000, YL-6121 (all are brand names) by Mitsubishi Chemical, or mixtures thereof; Bisphenol S-type epoxy resins, such as EBPS-200 by a Nippon Kayaku company, EPX-30 by an ADEKA company, and EXA-1514 (brand name) by a DIC company; Bisphenol A novolak-type epoxy resins, such as jER157S (trade name) by Mitsubishi Chemical Corporation; tetraphenylolethane-type epoxy resins such as YL-931 manufactured by Mitsubishi Chemical Corporation and Araldite 163 manufactured by Huntsman Japan Corporation (all are brand names); Heterocyclic epoxy resins, such as Araldite PT810 (trade name) by Huntsman Japan, and TEPIC (trademark) by Nissan Chemical Corporation; Diglycidyl phthalate resin, such as Nichiyo Corporation Blemmer (trademark) DGT; Tetraglycidyl xylenoyl ethane resin, such as ZX-1063 by the Shin-Nittetsu Sumikin Chemical company; Naphthalene group-containing epoxy resins such as ESN-190, ESN-360, HP-4032 manufactured by DIC, EXA-4750, and EXA-4700 manufactured by Nippon-Sumikin Chemicals; Epoxy resin which has dicyclopentadiene frame|skeleton, such as HP-7200 by DIC and HP-7200H; glycidyl methacrylate copolymerization type epoxy resins such as CP-50S and CP-50M manufactured by Nichiyu Corporation; Further, a copolymerized epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives (eg, PB-3600 manufactured by Daicel Chemical Industries, etc.), CTBN-modified epoxy resins (eg, YR-102 and YR-450 manufactured by Nippon Chemicals Co., Ltd.), etc. However, it is not limited to these. These epoxy resins can be used individually or in combination of 2 or more types.

Examples of the polyfunctional oxetane compound include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, 1,4-bis[ (3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl Acrylate, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate In addition to polyfunctional oxetanes such as their oligomers or copolymers, oxetane alcohol and novolac resin, poly(p-hydroxystyrene), cardo-type bisphenols, calixarenes, calixresorcin arenes or silces The etherified product with resin which has hydroxyl groups, such as quioxane, etc. are mentioned. In addition, the copolymer etc. of the unsaturated monomer which have an oxetane ring, and alkyl (meth)acrylate are mentioned.

As a compound which has a some cyclic thioether group in the said molecule|numerator, the bisphenol A episulfide resin YL7000 etc. by Mitsubishi Chemical Corporation are mentioned, for example. Moreover, the episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis|combining method can also be used.

(A) A thermosetting component is 1 mass % or more and 40 mass % or less with respect to the total mass (solid content) of a thermosetting composition, Preferably it is mix|blended in 1 mass % or more and 10 mass % or less. (A) By making a thermosetting component into the range of 1 mass % or more and 40 mass % or less with respect to the total mass (solid content) of a thermosetting composition, thermal conductivity improvement and coefficient of linear expansion (CTE) become low, and adhesiveness becomes favorable.

Moreover, when using the thermosetting component which has a some cyclic (thio) ether group in the said molecule|numerator as (A) thermosetting component, it is preferable to contain a thermosetting catalyst (curing catalyst). Examples of such a thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 4-phenylimidazole. imidazole derivatives such as , 1-cyanoethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; Amines 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; Phosphorus compounds, such as a triphenylphosphine, etc. are mentioned. In addition, commercially available ones include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ manufactured by Shikoku Chemical Co., Ltd. (all are trade names of imidazole-based compounds), U-CAT3503N manufactured by San-Apro, UCAT3502T ( All are brand names of dimethylamine block isocyanate compounds), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and their salts), etc. are mentioned. In particular, it is not limited to these, The thermosetting catalyst of an epoxy resin or an oxetane compound, or anything which accelerates|stimulates reaction of an epoxy group or an oxetanyl group and a carboxyl group may be used, You may use individually or in mixture of 2 or more types.

The compounding quantity of these curing catalysts is sufficient in a normal quantitative ratio, For example, 0.1 mass part or more and 10 mass parts or less are suitable per 100 mass parts of total of the said epoxy compound and/or an oxetane compound.

[(B) Aluminum oxide particles]

It is preferable that the (B) aluminum oxide particle used by this invention is spherical. By using a spherical aluminum oxide, a viscosity raise at the time of highly filling can be moderated. The average particle diameters of these aluminum oxide particles are 0.01 micrometer - 50 micrometers, More preferably, they are 0.01 micrometer - 20 micrometers. When the average particle diameter is smaller than 0.01 µm, the viscosity of the composition becomes too high, so that dispersion is difficult, and application to an object to be coated also becomes difficult. On the other hand, when an average particle diameter is larger than 50 micrometers, protrusion to a coating film will generate|occur|produce, and a sedimentation rate will become quick and storage stability will deteriorate. In addition, by blending two or more kinds of those having an average particle diameter having a particle size distribution for the closest packing, it is possible to further achieve high packing, which is preferable in terms of storage stability and thermal conductivity.

Here, in the present specification, (B) the average particle diameter of the aluminum oxide particles is the average particle diameter (d50) including not only the particle diameter of the primary particles but also the particle diameter of the secondary particles (aggregates), and d50 measured by the laser diffraction method is the value As a measuring apparatus by a laser diffraction method, the Microtrac MT3300EX11 manufactured by Nikkiso Co., Ltd. is mentioned.

(B) As a commercial item of aluminum oxide particle, DAW-05 (made by Denka, average particle diameter of 5 micrometers), DAW-10 (made by Denka, average particle diameter of 10 micrometers), AS-40 (made by Showa Denko, average particle diameter) 12 micrometers), AS-50 (The Showa Denko make, average particle diameter 9 micrometers), etc. are mentioned.

(B) Aluminum oxide particles can be blended in the range of 40 mass% or more and 95 mass% or less, preferably 50 mass% or more and 90 mass% or less, with respect to the total mass (solid content) of the thermosetting composition.

(B) the aluminum oxide particles can effectively lower the thermal conductivity of the cured film obtained by making it 40 mass % or more with respect to the total mass (solid content) of the thermosetting composition, and by making it 95 mass % or less, it is possible to increase the strength of the cured film do.

[Other Ingredients]

Moreover, antioxidant, an organic solvent, an antifoamer/leveling agent, a dispersing agent, and a coloring agent can be added to the thermosetting composition used by this invention.

An antioxidant improves the adhesiveness of a base material and the cured film of a thermosetting composition by suppressing oxidation of the conductor (copper) on a base material. Examples of the antioxidant include hindered phenol compounds such as 3-(N-salicilyl)amino-1,2,4-triazole, sulfur-based antioxidants such as zinc salt of 2-mercaptobenzimidazole, and triphenylphosphite. Hetero-dry compounds containing nitrogen as a hetero atom, such as phosphorus antioxidants, such as aromatic amine antioxidants, such as di-tert- butyldiphenylamine, melamine, benzotriazole, tolyltriazole, etc. are mentioned. Especially, a melamine and benzotriazole are preferable, and a melamine is especially preferable.

When the antioxidant is blended, the blending amount is 0.1 mass% or more and 5 mass% or less, preferably 0.5 mass% or more and 2 mass% or less, with respect to the total mass (solid content) of the thermosetting composition used in the present invention.

The organic solvent can be used for adjusting the thermosetting composition used in the present invention or for adjusting the viscosity for application to a substrate.

As the organic solvent, any known organic solvent can be used, and specific examples include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. can More specifically, Ketones, such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether , glycol ethers such as triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene 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, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These organic solvents may be used individually by 1 type, and may be used as a 2 or more type mixture.

An antifoaming agent and a leveling agent can be mix|blended in order to prevent deterioration of surface smoothness, and to prevent deterioration of the interlayer insulation by a void or a pinhole. Examples of the defoaming agent (leveling agent) include a silicone-based anti-foaming agent and a non-silicone-based anti-foaming agent that is a foaming polymer solution. -066N, BYK (trademark) -067A, BYK (trademark)-077 (above, the Big Chemi Japan company make), KS-66 (Shin-etsu Chemical Co., Ltd. make) etc. are mentioned.

In addition, commercially available products of non-silicone antifoaming agents include BYK (registered trademark)-054, BYK (registered trademark)-055, BYK (registered trademark)-057, BYK (registered trademark)-1790, BYK (registered trademark)-1791 (above , Big Chemie Japan) etc. are mentioned.

When an antifoaming agent (leveling agent) is blended, the blending amount is 10 mass % or less, preferably 0.01 mass % or more and 3 mass % or less, with respect to the total mass (solid content) of the thermosetting composition used in the present invention.

A dispersing agent can be mix|blended in order to improve the dispersibility and settling property of (B) aluminum oxide particle.

As a commercial item of a dispersing agent, For example, 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, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183, DISPERBYK-185, DISPERBYK-184, DISPERBYK-184 2000, DISPERBYK-2001, DISPERBYK-2009, DISPERBYK-2020, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2096, DISPERBYK-2150, BYK-P104, BYK-P104S, BYK-P105, BYK-9076, BYK-9077, BYK-220S (above, made by Big Chemie Japan), Dispalon 2150, Dispalon 1210, Dispalon KS-860, Dispalon KS-873N, Dispalon 7004, Dispalon 1830, Dispalon 1860, Dispalon 1860 Palon 1850, Dispalon DA-400N, Dispalon PW-36, Dispalon DA-703-50 (above, manufactured by Kusumoto Kasei), Floren G-450, Floren G-600, Floren G-820, Floren G-700, Floren DOPA-44, and Floren DOPA-17 (made by Kyoesha Chemical) are mentioned.

When a dispersing agent is mix|blended, the compounding quantity is 0.1 mass part or more and 10 mass parts or less with respect to 100 mass parts (solid content) of (B) aluminum oxide particle, Preferably they are 0.1 mass part or more and 5 mass parts or less.

As the colorant, a commonly known colorant such as red, blue, green, or sulfur can be used, and any of a pigment, a dye, and a colorant may be used. Specifically, a color index (C.I.; published by The Society of Dyers and Colorists) numbered can be exemplified. However, it is preferable that it is a coloring agent which does not contain a halogen from a viewpoint of environmental load reduction and an influence on a human body.

Examples of the red colorant include monoazo, disazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone.

As a blue colorant, there exist a phthalocyanine type and an anthraquinone type, there exist the compounds classified into the pigment type as a pigment type, In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

As a green coloring agent, there exist a phthalocyanine type, an anthraquinone type, and a perylene type similarly, In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone.

In addition, you may add colorants, such as purple, orange, brown, and black, for the purpose of adjusting color tone.

In addition, if necessary, well-known and customary additives such as known and customary polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, and phenothiazine, flame retardants, and flame retardant auxiliary agents are blended. can do.

<struct>

The structure of the present invention has a cured film of the above thermosetting composition formed on an LCP substrate.

In the present invention, the LCP substrate may be an injection-molded article having a complicated shape, or a wiring pattern (electric circuit) may be formed on the surface thereof.

As a formation method of the wiring pattern on such an injection-molded object, the LDS(Laser Direct Structuring) method is mentioned, for example. In the LDS method, a copper complex is first kneaded into a thermoplastic resin, injection-molded, and laser drawing is performed on the molded object surface containing this copper complex. A copper complex is metallized by laser beam irradiation, the catalytic activity of electroless copper plating is expressed, and plating of a laser drawing part is attained.

On this LCP substrate, the thermosetting composition used in the present invention is adjusted to a viscosity suitable for the coating method with, for example, the organic solvent, dip coating method, flow coating method, roll coating method, bar coater method, screen printing method , a coating film of a tack-free coating is formed by applying by a method such as a curtain coating method, and volatilizing and drying (temporarily drying) the organic solvent contained in the composition at a temperature of about 60 to 130°C.

The volatilization drying performed after the thermosetting composition used in the present invention is applied is a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, etc. It can carry out using the method of making countercurrent contact, and the method of spraying from a nozzle to a support body).

By heating this coating film to the temperature of about 140-180 degreeC and thermosetting, for example, the covering base material which concerns on this invention by which the cured film is formed on the LCP base material is obtained.

The coated base material having an electric circuit is then exposed to a land to be soldered by a laser opening, and the land is subjected to surface treatment by a gold plating treatment, and then components are mounted by soldering.

Soldering may be performed by any of hand soldering, flow soldering, and reflow soldering. For example, in the case of reflow soldering, preheating is performed at 100°C to 140°C for 1 to 4 hours, and thereafter, 240°C or higher to 270°C or higher. It is carried out by a reflow step in which the solder is heated and melted by repeating heating for about 5 to 20 seconds at a temperature of less than °C a plurality of times (eg, 2 to 4 times).

After a reflow process, it cools, a component is mounted, and a three-dimensional circuit molded part (MID) is completed.

The coated substrate of the present invention, that is, the coated substrate having a cured film of the thermosetting composition used in the present invention on the LCP substrate, is applicable to various uses in that it is excellent in heat resistance, rigidity, adhesion to a substrate, and insulation, and is applicable There is no particular limitation on the subject. For example, a coated substrate having an etching resist, a soldering resist, and a marking resist as a cured film can be prepared on an injection-molded LCP substrate, and among them, high heat resistance is required because solderability is improved. The coating base material which has a soldering resist as a cured film can be manufactured suitably.

Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not limited only to these Examples. In addition, unless otherwise indicated below, "part" shall mean a mass part.

Example

1. Preparation of thermosetting compositions of Examples 1 to 3 and Comparative Examples 1 to 2

Each material was respectively blended and premixed with a stirrer at the ratios (unit: parts by mass) shown in Table 1, and then kneaded with a three-roll mill to prepare a thermosetting composition.

The characteristic test shown below was done about each said thermosetting composition. The results are shown in Table 1.

2. Evaluation

(1) Solder heat resistance

The thermosetting compositions of Examples and Comparative Examples were printed on an LCP substrate (TECACOMP LCP LDS 4107 manufactured by Ensinger) so that the dry coating film was about 30 μm by screen printing, and cured at 150° C. for 60 minutes. A rosin-based flux was applied on the coating film of the obtained substrate, flowed for 10 seconds in a solder bath at 260° C., washed and dried with propylene glycol monomethyl ether acetate, and then applied to a transparent adhesive tape (manufactured by Nichiban Corporation, width: 18 mm). The peel test was performed to evaluate the presence or absence of peeling. Those in which peeling did not occur were denoted as ○, and those in which peeling occurred were denoted by ×. In addition, the load deflection temperature (DTUL) based on ASTM D648 (1.82 MPa) of the LCP substrate is 274 °C.

(2) Adhesion (tape test)

The thermosetting compositions of Examples and Comparative Examples were pattern-printed on the same LCP substrate as above so that the dry coating film was about 30 μm by screen printing, and cured at 150° C. for 60 minutes. The peel test by a transparent adhesive tape (made by Nichiban Corporation, width: 18 mm) was done on the film of the obtained board|substrate, and adhesiveness was evaluated. Those in which peeling did not occur were denoted as ○, and those in which peeling occurred were denoted by ×.

*1: cresol novolak type epoxy resin, epoxy equivalent 209 to 219 (g/eq) (N-695: manufactured by DIC)

*2: Spherical aluminum oxide with an average particle diameter of about 8 µm (DAW-07: manufactured by Denka Corporation)

*3: Spherical aluminum oxide with an average particle diameter of about 3 µm (DAW-03: manufactured by Denka Corporation)

*4: Spherical aluminum oxide with an average particle diameter of about 0.3 µm (ASFP-20: manufactured by Denka Corporation)

*5: barium sulfate (B-30: manufactured by Sakai Chemical Kogyo Co., Ltd.)

*6: Talc (LMS-200: Fuji Talc Kogyo Co., Ltd.)

*7: Particulate silica (Nippon Aerosil Co., Ltd. R-974)

*8: dicyandiamide (DICY7: manufactured by Mitsubishi Chemical Corporation)

*9: 2-ethyl-4-methylimidazole (2E4MZ: Shikoku Chemical Co., Ltd.)

*10: fine powder melamine (melamine: manufactured by Nissan Chemical Corporation)

*11: dipropylene glycol monoethyl ether

*12: Silicone-based antifoaming agent (KS-66: manufactured by Shin-Etsu Chemical Co., Ltd.)

*13: Non-silicone antifoaming agent (BYK-1791: Big Chemie Japan Co., Ltd.)

*14: Dispersing agent (BYK-111: made by Big Chemie Japan)

As shown in Examples 1 to 3 of Table 1, when (B) aluminum oxide particles were blended, the thermosetting composition to the liquid crystal polymer substrate was excellent in both hardened layer adhesion and solder heat resistance, and peeling was not recognized. Confirmed.

On the other hand, as shown in Comparative Examples 1 and 2, when other inorganic fillers were used instead of aluminum oxide particles, it was recognized that adhesiveness and heat resistance were inferior.

Claims (3)

A structure comprising: a substrate composed of a liquid crystal polymer; and a cured film of a thermosetting composition formed on the surface of the substrate;
The thermosetting composition,
(A) a thermosetting component;
(B) aluminum oxide particles
A structure comprising a. The liquid crystal polymer according to claim 1, wherein the liquid crystal polymer has the following formulas (a) and/or (b)

A structure, characterized in that it is a liquid crystal polyester resin comprising a repeating unit represented by, or a wholly aromatic liquid crystal polyester resin composed of the repeating unit. The structure according to claim 1 or 2, wherein the substrate made of the liquid crystal polymer has a deflection temperature under load (DTUL) of 140° C. or more and 350° C. or less based on ASTM D648 (1.82 MPa).