TWI833019B - Thermosetting composition and coated base material having its cured film - Google Patents

Abstract

The object of the present invention is to provide a thermosetting composition for surface coating of a high-melting-point substrate, which can solve the problem of coating film peeling when applied to a high-melting-point substrate, and to provide a thermosetting composition for applying thermal hardening to a high-melting-point substrate. The coating base material of the surface coating layer of the sexual composition. The solution is a thermosetting composition for coating on a high-melting-point base material having a melting point of 270° C. or higher, and which contains: (A) a thermosetting component, (B) an oxidizing component Aluminum particles, and (C) an acrylic block copolymer represented by the following formula (I) or the following formula (II), or (In the formula, X and Polymer block) The mass percentage of the sum of X and A coated substrate formed on a high melting point substrate.

Description

Thermosetting composition and coated base material having its cured film

The present invention relates to a thermosetting composition and a coated substrate having a cured film thereof, and in particular to a thermosetting composition for coating on a high melting point substrate and a coated substrate having a cured film thereof.

In the past, conductor patterns were formed on planar substrates such as copper-clad laminated plates such as phenol paper and epoxy paper, glass substrates, ceramic substrates, and wafer plates. However, since liquid crystal polymers (LCP), polyether ether ketone It seems that high-temperature thermoplastic super engineering plastics such as (PEEK) and polyphenylene sulfide (PPS) have the heat resistance to withstand the heating of the reflow step when mounting parts on printed circuit boards. In recent years, three-dimensional molded products of super engineering plastics have been used as Substrates for circuit formation were brought up for review. In addition, three-dimensional circuit molded parts in which circuits are formed on the base material of the three-dimensional molded product and components are mounted are called MID (Molded Interconnect Device).

Patent Document 1 discloses an invention in which a three-dimensional molded article of a heat-resistant thermoplastic resin such as liquid crystal polymer (LCP) or polyetheretherketone (PEEK) is coated with a thermosetting resin such as epoxy resin. Complete MID substrate.

According to the MID obtained using the substrate of Patent Document 1, a circuit can be formed on the surface of a small and complex three-dimensional molded object. Therefore, it is possible to manufacture products that comply with the trend of electronic components that are light, thin and short. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2018-115355

[Problem to be solved by the invention]

However, examination by the inventors revealed that super engineering plastics such as liquid crystal polymer (LCP) and polyether ether ketone (PEEK) have high glass transition points (Tg) and low thermal expansion coefficients (CTE). Therefore, if conventional plastics are If the resin composition of the solder resist is coated on the surface of the super engineering plastic, the resulting solder resist film may peel off due to poor CTE. In this regard, it is thought that the hardness of the coating film that cannot absorb shrinkage caused by poor CTE may also be a factor.

Generally speaking, when the CTE difference between the base material and the resin composition covering the base material causes a problem, it is known that the CTE difference can be suppressed by increasing the blending amount of the inorganic filler in the resin composition. However, There is no review at all on the use of high melting point materials such as super engineering plastics as base materials.

The present invention was made in view of the above problems, and its purpose is to provide a thermosetting composition for surface coating of a high-melting-point substrate that can solve the problem of peeling of the coating film when applied to the high-melting-point substrate, and to provide A coated base material in which a surface coating layer of a thermosetting composition is applied to a high melting point base material. [Means used to solve problems]

The inventors of the present invention have made intensive studies to achieve the above object. As a result, it was found that by blending alumina and a block copolymer having a polymer block mainly composed of a predetermined proportion of methacrylate units in a thermosetting composition, the peeling of the coating film from the high-melting-point substrate can be solved. problem to complete the present invention.

That is to say, it was found that the above object of the present invention can be achieved by a thermosetting composition for coating on a high melting point base material having a melting point of 270° C. or higher, which is characterized by containing : (A) thermosetting component, (B) alumina particles, and (C) an acrylic block copolymer represented by the following formula (I) or the following formula (II), (In the formula, X and Polymer block) The mass percentage of the sum of X and

In the thermosetting composition of the present invention, it is further preferred that the weight average molecular weight of (C) the acrylic block copolymer is 65,000 or more and 80,000 or less.

In addition, the acrylic block copolymer (C) is preferably an acrylic block copolymer represented by the aforementioned formula (I). In the aforementioned formula (I), X is a polymer mainly composed of methyl methacrylate units. As for the block, Y is a polymer block mainly composed of n-butyl acrylate units.

Furthermore, the amount of (B) alumina particles is preferably 40 mass% or more and 90 mass% or less based on the total mass of the thermosetting composition.

In addition, the amount of (C) the acrylic block copolymer is preferably 0.5 mass % or more and 20 mass % or less based on the total mass of the thermosetting composition.

In addition, ideally, the high melting point base material is selected from the group consisting of liquid crystal polymers, polyphenylene sulfide, and polyether ether ketone.

The above object of the present invention can also be achieved by a coated substrate characterized by: a cured film having the thermosetting composition of the present invention. [Effects of the invention]

According to the present invention, when a thermosetting composition is coated on a high-melting-point base material, the resulting cured film can be prevented from cracking, and the problem of peeling of the cured film from the high-melting-point base material can be solved.

＜Thermosetting composition＞

The thermosetting composition of the present invention is a thermosetting composition for coating on a high-melting-point base material having a melting point of 270° C. or higher, and contains: (A) a thermosetting component, (B) alumina particles, and (C) an acrylic block copolymer represented by the following formula (I) or the following formula (II), (In the formula, X and Polymer block) The mass percentage of the sum of X and

The thermosetting composition of the present invention can be used to coat a high melting point substrate having a melting point of 270° C. or above.

Regarding the base material, since the conductor pattern is formed and then it must withstand the heat when parts are mounted by reflow or flow soldering, a high melting point having a melting point of 270°C or higher, preferably 300°C or higher, particularly preferably 330°C or higher, is used. Melting point substrate.

In the present invention, the melting point (melting temperature) of the high-melting-point base material means the temperature measured in accordance with JIS K 7121 using a differential scanning calorimeter.

Examples of materials for the high-melting-point base material having a melting point of 270° C. or higher include polyetheretherketone, liquid crystal polymer, and polyphenylene sulfide. In these materials, inorganic fillers can also be added as necessary, or used together with glass cloth. Examples of the inorganic filler include fibrous inorganic fillers such as glass fiber and carbon fiber, short fiber fillers (whiskers such as silicon carbide, silicon nitride, zinc oxide, etc.), and plate-shaped inorganic fillers such as talc and mica.

When adding a fibrous inorganic filler, its shape is preferably such that the fiber diameter is in the range of 6 to 15 μm and the aspect ratio is in the range of 5 to 60. When a plate-shaped inorganic filler is used, the plate-shaped inorganic filler preferably 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. .

The fibrous inorganic filler, the short fibrous filler (whisker), and the plate-like inorganic filler can be used individually or in combination of two or more types. In addition, powdery or needle-like inorganic fillers can be added. In addition, carbon black and the like can also be added as a colorant to a high melting point base material having a melting point of 270° C. or higher.

In particular, liquid crystal polymer is preferably used as a material for a high melting point base material having a melting point of 270° C. or higher from the viewpoint of formability, electrical properties, and chemical resistance.

The liquid crystal polymer used in the high melting point base material of the present invention, as long as it is polyester or polyesteramide that forms an anisotropic melt phase, is called thermotropic liquid crystal polyester or thermotropic liquid crystal polyester in this technical field. The esteramide is not particularly limited.

The nature of the anisotropic melt phase can be confirmed by conventional polarization inspection using crossed polarizers. Specifically, the anisotropic melt phase can be confirmed by using a Leitz polarizing microscope to observe the sample placed on the Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times. The liquid crystal polymer used in the high melting point substrate of the present invention exhibits optical anisotropy, that is, it allows light to pass through when inspected between crossed polarizers. If the sample is optically anisotropic, polarized light will pass through it even in a stationary state.

Examples of the polymerizable monomer constituting the liquid crystal polymer include aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic aminocarboxylic acid, aromatic hydroxylamine, aromatic diamine, and aliphatic diamine. Alcohols and aliphatic dicarboxylic acids. The liquid crystal polymer may be a homopolymer of one of these polymerizable monomers or a copolymer of two or more polymerizable monomers, and preferably contains at least one polymerizable monomer having a hydroxyl group and a carboxyl group as a constituent component.

In addition, the polymerizable monomer constituting the liquid crystal polymer may be an oligomer in which one or more of the compounds exemplified above are bonded.

From the viewpoint of excellent fluidity and mechanical properties, the liquid crystal polymer is preferably a liquid crystal polyester resin containing repeating units represented by formula (a) and/or formula (b), or a liquid crystal polyester resin composed of the same repeating units. Aromatic liquid crystal polyester resin.

The thermosetting composition of the present invention is particularly suitable for use when a high melting point base material is injection molded and a conductive pattern is formed on the base material. Furthermore, when a three-dimensional molded product of an injection-molded high-melting-point base material is used as a base material for forming a conductive pattern, the high-melting-point base material is also required to maintain rigidity even when heated at high temperatures.

Specifically, the deflection temperature under load (DTUL) of the high-melting-point base material is based on ASTM D648 (1.82MPa) (the specification number of the ASTM specifications established and published by ASTM International (formerly known as the American Society for Testing and Materials: American Society for Testing and Materials)). ) is above 140°C and below 350°C, preferably above 180°C and below 310°C, particularly preferably above 200°C and below 290°C.

By setting the load deflection temperature of the high-melting-point base material to 140°C or more and 350°C or less, deformation will not occur even during heating during welding, and the molding process will be easy.

A specific example of measurement of the deflection temperature under load (DTUL) is disclosed below, taking the case of a liquid crystal polymer as an example.

An injection molding machine (manufactured by Nissei Plastics Industry Co., Ltd., UH1000-110) was used for injection molding at a cylinder temperature of crystal melting temperature + 20 to 40°C and a metal mold temperature of 70°C to produce a strip-shaped test piece (length 127 mm × width 12.7 mm × thickness 3.2mm). Using this test piece, according to ASTM D648, the temperature when reaching the predetermined deflection amount (0.254mm) is measured with a load of 1.82MPa and a heating rate of 2°C/min.

Examples of these commercially available high-melting base materials having a melting point of 270°C or higher and a load deflection temperature of 140°C to 350°C include Vectra (registered trademark) E841iLDS and Vectra (registered trademark) E840iLDS (the above is Celanese Japan Co., Ltd.), TECACOMP (registered trademark) LCP LDS black4107 (manufactured by Ensinger Co., Ltd.), RTP 3499-3 X 113393A (manufactured by RTP Co., Ltd.), etc. In addition, the high-melting-point base material having a melting point of 270° C. or higher and a load deflection temperature of 140° C. or higher and 350° C. or lower is also sold by Ueno Pharmaceutical Co., Ltd.

[(A) Thermosetting component] The thermosetting component is a compound added to thermally harden the thermosetting composition of the present invention.

As the thermosetting component used in the present invention, amine resins such as melamine resin and benzoguanamine resin, polyisocyanate compounds, blocked isocyanate compounds, cyclic carbonate compounds, polyfunctional epoxy compounds, and polyfunctional oxygen heterocycles can be used. Well-known and commonly used thermosetting resins such as butane compounds, episulfide resins, melamine derivatives, benzoguanamine derivatives, bismaleimide, oxazine compounds, oxazoline compounds, carbodiimide compounds, etc. . Particularly preferred are thermosetting components having a plurality of cyclic ether groups or cyclic thioether groups (hereinafter abbreviated as "cyclic (thio)ether groups") in the molecule.

This kind of thermosetting component with multiple cyclic (thio)ether groups in the molecule is any one or both of cyclic ether groups with multiple 3, 4 or 5-membered rings or cyclic sulfide groups in the molecule. Examples of compounds with such groups include compounds having multiple epoxy groups in the molecule, that is, polyfunctional epoxy compounds, and compounds having multiple oxetanyl groups in the molecule, that is, polyfunctional oxetane Alkane compounds, compounds with multiple thioether groups in the molecule, that is, episulfide resins, etc.

Examples of the polyfunctional epoxy compounds include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, EHPE3150 manufactured by DAICEL Chemical Industries, Ltd., EPICLON 840, EPICLON 850, EPICLON 1050, EPICLON 2055 manufactured by DIC Corporation, and Nippon Steel & Sumitomo Metal Co., Ltd. EPOTOTE YD-011, YD-013, YD-127, YD-128 made by Chemical Company, D.E.R. 317, D.E.R. 331, D.E.R. 661, D.E.R. 664 made by Dow Chemical Company, Araldite 6071, Araldite 6084, Araldite GY250 made by Huntsman Japan Company , Araldite GY260, bisphenol A-type epoxy resins such as SUMIEPOXY ESA-011, ESA-014, ELA-115, ELA-128 (any of which are trade names) manufactured by Sumitomo Chemical Industries, Ltd.; manufactured by Mitsubishi Chemical Corporation jERYL903, EPICLON 152 and EPICLON 165 manufactured by DIC Corporation, EPOTOTE YDB-400 and YDB-500 manufactured by Nippon Steel and Sumitomo Metal Chemical Corporation, D.E.R. 542 manufactured by Dow Chemical Corporation, Araldite 8011 manufactured by Huntsman Japan Corporation, and Sumitomo Chemical Industries Corporation Brominated epoxy resins such as SUMIEPOXY ESB-400 and ESB-700 (all are trade names); jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, D.E.N. 431 and D.E.N. 438 manufactured by Dow Chemical Company, and DIC Corporation EPICLON N-730, EPICLON N-770, EPICLON N-865, EPOTOTE YDCN-701, YDCN-704 manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., Araldite ECN1235, Araldite ECN1273, Araldite ECN1299, Araldite XPY307 manufactured by Huntsman Japan, Japan EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000 manufactured by Chemical Industry Co., Ltd., SUMIEPOXY ESCN-195X, ESCN-220, ECN-235, ECN- manufactured by Sumitomo Chemical Industries, Ltd. Phenol-type epoxy resins of class 299 (any of which are trade names); EPICLON 830 manufactured by DIC Corporation, jER807 manufactured by Mitsubishi Chemical Corporation, EPOTOTE YDF-170, YDF-175, YDF- manufactured by Nippon Steel and Sumitomo Metal Chemical Corporation 2004. Bisphenol F-type epoxy resins such as Araldite Name) and other hydrogenated bisphenol A-type epoxy resins; jER604 manufactured by Mitsubishi Chemical Corporation, EPOTOTE YH-434 manufactured by Nippon Steel and Sumitomo Metal Chemical Corporation, Araldite MY720 manufactured by Huntsman Japan Corporation, SUMIEPOXY ELM- manufactured by Sumitomo Chemical Industries, Ltd. Glycidylamine-type epoxy resins such as 120 (any of which are trade names); hydantoin-type epoxy resins such as Araldite CY-350 (trade name) manufactured by Huntsman Japan; CELLOXIDE manufactured by DAICEL Chemical Industry Co., Ltd. 2021. Alicyclic epoxy resins such as Araldite CY175 and CY179 (any of which are trade names) manufactured by Huntsman Japan; YL-933 manufactured by Mitsubishi Chemical Company, EPPN-501 and EPPN- manufactured by Nippon Chemical Company Trishydroxyphenylmethane type epoxy resins such as 502 (any of which are trade names); YL-6056, YX-4000, YL-6121 (any of which are trade names) manufactured by Mitsubishi Chemical Corporation, etc. Xylenol type or biphenol type epoxy resin or a mixture of these; bisphenol S-type rings such as EBPS-200 made by Nippon Kayaku Co., Ltd., EPX-30 made by ADEKA Co., Ltd., EXA-1514 (trade name) made by DIC Co., Ltd. Oxygen resin; Bisphenol A novolac-type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Company; YL-931 manufactured by Mitsubishi Chemical Company, Araldite 163 manufactured by Huntsman Japan Company, etc. (either one is a trade name) tetrahydroxyphenylethane type epoxy resin; heterocyclic epoxy resins such as Araldite PT810 (trade name) manufactured by Huntsman Japan, TEPIC (registered trademark) manufactured by Nissan Chemical Co., Ltd.; BLEMMER (trade name) manufactured by NOF Corporation Registered trademark) diglycidyl phthalate resin such as DGT; tetraglycidyl xylyl ethane resin such as ZX-1063 manufactured by Nippon Steel and Sumitomo Metal Chemicals Co., Ltd.; ESN-190 manufactured by Nippon Steel and Sumitomo Metal Chemical Co., Ltd. , ESN-360, naphthyl-containing epoxy resins such as HP-4032, EXA-4750, and EXA-4700 made by DIC; HP-7200, HP-7200H made by DIC, etc. have a dicyclopentadiene skeleton. Epoxy resins; glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M manufactured by NOF Corporation; in addition, there are also cyclohexyl maleimide and glycidyl methacrylate copolymerized epoxy resin; epoxy-modified polybutadiene rubber derivatives (such as PB-3600 manufactured by DAICEL Chemical Industry, etc.), CTBN modified epoxy resin (such as YR-102, YR manufactured by Nippon Steel and Sumitomo Metal Chemical Co., Ltd. -450, etc.) are not limited to these products. These epoxy resins can be used individually or in combination of 2 or more types.

The aforementioned polyfunctional oxetane compounds include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxa) cyclobutanylmethoxy)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-oxoacrylate) Hetetanyl)methyl ester, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate In addition to polyfunctional oxetanes such as their oligomers or copolymers, there are also oxetane alcohols and phenolic resins, poly(p-hydroxystyrene), cardo-type bisphenols, and calixarenes. etherates of resins such as calixresorcin aromatics, or sesquisiloxane and other resins having hydroxyl groups. Other examples include copolymers of unsaturated monomers having an oxetane ring and alkyl (meth)acrylates.

Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. In addition, the same synthesis method can be used, and an episulfide resin in which the oxygen atom of the epoxy group of the novolac-type epoxy resin is replaced with a sulfur atom can also be used.

(A) The thermosetting component can be blended in a range of 1 to 10 mass%, preferably 1 to 5 mass%, based on the total mass (solid content) of the thermosetting composition. combine. By setting (A) the thermosetting component in the range of 1 mass % or more and 10 mass % or less with respect to the total mass (solid content) of the thermosetting composition, the coefficient of linear expansion (CTE) becomes low and the adhesion improves. good.

In addition, when the thermosetting component (A) having a plurality of cyclic (thio)ether groups in the molecule is used, it is preferable to contain a thermosetting catalyst (curing catalyst). Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and 1-cyanohydrin. Imidazole derivatives such as ethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyanodiamide, benzyldimethylamine, 4 -(Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzyl Amine compounds such as hydroxyamine, hydrazine compounds such as adipic acid dihydrazide and secretic acid dihydrazide, etc.; phosphorus compounds such as triphenylphosphine, etc. In addition, commercially available products include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ manufactured by Shikoku Chemical Industry Co., Ltd. (all of which are trade names of imidazole compounds), and U manufactured by San Apro Corporation. -CAT3503N, UCAT3502T (both are trade names of dimethylamine blocked isocyanate compounds), DBU, DBN, U-CATSA102, U-CAT5002 (both are bicyclic amidine compounds and their salts), etc. It is not particularly limited to these products, as long as it is a thermosetting catalyst for epoxy resin or oxetane compound or promotes the reaction between epoxy group or oxetane group and carboxyl group, it can be used alone or in combination. Use a mix of the above.

The blending amount of these curing catalysts is sufficient to be a normal amount ratio, for example, 0.1 to 10 parts by mass per 100 parts by mass of the total of the aforementioned epoxy compounds and/or oxetane compounds is appropriate. As long as the blending amount of the curing catalyst is within this range, the curing properties will be good and the service life will be long.

[(B) Aluminum oxide particles] The (B) alumina particles used in the present invention are preferably spherical. By using spherical alumina, the viscosity rise at high filling can be mitigated. The average particle diameter of such alumina particles is 0.01 μm to 50 μm, preferably 0.01 μm to 20 μm. If the average particle diameter is less than 0.01 μm, the viscosity of the composition becomes too high, making it difficult to disperse and apply to an object to be coated. On the other hand, if the average particle diameter exceeds 50 μm, a coating film will appear, the sedimentation speed will become faster, and the storage stability will deteriorate. In addition, by blending particles with two or more average particle sizes having the most densely packed particle size distribution, higher filling can be achieved, which is suitable from both the viewpoints of storage stability and thermal conductivity.

Here, in this specification, the average particle diameter of (B) alumina particles includes not only the particle diameter of primary particles but also the average particle diameter (d50) of the particle diameter of secondary particles (aggregates). The value of d50 measured by the radiation diffraction method. An example of a measuring device using the laser diffraction method is Microtrac MT3300EX11 manufactured by Nikkiso Co., Ltd.

(B) Commercially available products of alumina particles include DAW-05 (manufactured by Denka Co., Ltd., average particle diameter: 5 μm), DAW-10 (manufactured by Denka Co., Ltd., average particle diameter: 10 μm), and AS-40 (manufactured by Showa Denko Co., Ltd., average particle size: 12 μm), AS-50 (manufactured by Showa Denko, average particle size: 9 μm), etc.

(B) Alumina particles can be blended in a range of 40 mass % to 95 mass %, preferably 60 mass % to 95 mass %, based on the total mass (solid content) of the thermosetting composition. .

(B) Alumina particles can be blended in a range of 40 mass % to 95 mass %, preferably 60 mass % to 95 mass %, relative to the total mass (solid content) of the thermosetting composition.

By setting (B) the alumina particles to 40 mass % or more relative to the total mass (solid content) of the thermosetting composition, the thermal conductivity of the obtained cured film can be effectively reduced. By setting it to 95 mass % % or less can improve the strength of the hardened film.

[(C) Acrylic block copolymer] (C) The acrylic block copolymer is blended for the purpose of improving the adhesion of the cured film of the thermosetting composition of the present invention to a high melting point substrate and improving the heat resistance.

Block copolymer refers to a copolymer in which two or more polymers with different properties are connected by covalent bonds to form a long-chain molecular structure. It is preferably solid in the range of 20°C to 30°C. As long as it is a solid within this range, it may also be a solid at temperatures outside this range. Since it is solid in the above temperature range, it exhibits excellent adhesion when applied to a substrate and pre-dried.

The (C) acrylic block copolymer used in the present invention is an X-Y-X or X-Y-X' type terpolymer. Among the X-Y-X or High, preferably composed of polymer units above 0°C. The glass transition point Tg can be measured by differential scanning calorimetry (DSC).

In addition, in the X-Y-X or X-Y-X' type (C) acrylic block copolymer, X and The result is better.

In addition, among the X-Y-X or X-Y-X' type (C) acrylic block copolymers, X and It is better if the compatibility of sexual ingredients is low. It is thought that a block copolymer in which the blocks at both ends are soluble in the matrix and the central block is incompatible with the matrix can easily develop a specific structure in the matrix.

X and X' are polymer blocks mainly composed of methacrylate units, and are polymer blocks mainly composed of methacrylate units. In addition, mainly composed of methacrylate units means that it contains 50 mass % or more of structural units derived from methacrylate, calculated based on the total mass of polymer blocks X and X'. The proportion of structural units derived from methacrylate contained in X and X' is preferably 60 mass% or more in the polymer blocks X and Mass %.

Methacrylates used to form polymer blocks X and X' include, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and third Alkyl methacrylates such as tributyl ester, cyclohexyl methacrylate, isobornyl methacrylate, etc., and methyl methacrylate is particularly preferred. The polymer blocks X and X' may be composed of one kind or two or more kinds of these methacrylates.

Y is a polymer block mainly composed of acrylate units, and is a polymer block mainly composed of acrylate units. In addition, "mainly composed of acrylate units" means that it contains 50 mass % or more of structural units derived from acrylic esters, calculated based on the total mass of the polymer block Y. The proportion of structural units derived from acrylate contained in Y is preferably 60 mass % or more in the polymer block Y, more preferably 80 mass % or more, and may be 100 mass %.

In addition, a hydrophilic structural unit having excellent compatibility with (A) the thermosetting component such as the aforementioned epoxy resin may be introduced into the structural units of X and/or X'. This can further improve compatibility. Examples of the hydrophilic structural unit here include styrene units, hydroxyl group-containing structural units, carboxyl group-containing structural units, epoxy-containing structural units, N-substituted acrylamide structural units, and the like.

Examples of the acrylate used to form the polymer block Y include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, and phenoxy acrylate. Among the alkyl acrylates such as ethyl acrylate and 2-methoxyethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate are preferred, and n-butyl acrylate is particularly preferred. The polymer block Y may be composed of one kind of these acrylates, or two or more kinds thereof.

When the (C) acrylic block copolymer is of the X-Y-X type, the mass percentage of 30 quality or less. In addition, when the (C) acrylic block copolymer is of the X-Y-X' type, the mass percentage of the sum of X and X' is 12 mass % or more relative to the total mass of the (C) acrylic block copolymer. 35 mass% or less, preferably 15 mass% or more and 30 mass% or less.

By setting these mass percentages to 12 mass % or more and 35 mass % or less, when the thermosetting composition of the present invention is coated on a high melting point base material and then cured, it is possible to obtain a composition while ensuring adhesion to the high melting point base material. Cured coating with excellent heat resistance.

(C) Commercially available products of acrylic block copolymers include KURARITY (registered trademark) LA2250, KURARITY (registered trademark) LA2140, KURARITY (registered trademark) LA2330, KURARITY (registered trademark) LA3320, and KURARITY (registered trademark) KL -LK9333, KURARITY (registered trademark) LK-9243 (the above are manufactured by Kuraray Corporation), etc.

(C) The method for producing the acrylic block copolymer is not particularly limited, and methods based on known methods can be used. Generally, a method such as living polymerization of monomers constituting each block is used.

(C) The weight average molecular weight of the acrylic block copolymer is in the range of 20,000 to 400,000, preferably in the range of 67,000 to 79,000. As long as it is within this range, a thermosetting composition can be obtained that is coated on a base material and exhibits excellent adhesion after predrying, as well as excellent printability and processability.

(C) The blending amount of the acrylic block copolymer is 0.5 mass % or more and 20 mass % or less based on the total mass (solid content) of the thermosetting composition, preferably 0.5 mass % or more and 10 mass % or less. , particularly preferably in the range of 0.5 mass% or more and 5 mass% or less.

By setting the blending amount of (C) the acrylic block copolymer to 0.5% by mass or more and 20% by mass or less based on the total mass (solid content) of the thermosetting composition, the proportion of the thermosetting resin can be reduced. The connection density remains at a high level.

[Other ingredients] In addition, antioxidants, organic solvents, defoaming agents, leveling agents, dispersants, and colorants may be added to the thermosetting composition of the present invention.

Antioxidants improve the adhesion between the base material and the cured film of the thermosetting composition by inhibiting the oxidation of the conductor (copper) on the base material. Examples of antioxidants include hindered phenol compounds such as 3-(N-mercaptobenzimidazole)amino-1,2,4-triazole, sulfur-based antioxidants such as zinc salts of 2-mercaptobenzimidazole, and triphenylphosphorous acid. Phosphorus-based antioxidants such as esters, aromatic amine-based antioxidants such as di-tert-butyldiphenylamine, etc. Heterocyclic formulas containing nitrogen as heteroatoms such as melamine, benzotriazole, methylbenzotriazole, etc. Compounds etc. In particular, melamine and benzotriazole are preferred, and melamine is particularly preferred.

When blending an antioxidant, the blending amount is preferably 0.03 mass% or more and 5 mass% or less, preferably 0.1 mass% or more and 2 mass% or less based on the total mass (solid content) of the thermosetting composition of the present invention. .

The organic solvent can be used to prepare the thermosetting composition of the present invention or to adjust the viscosity required for coating on a substrate. As long as the organic solvent is a well-known organic solvent, any organic solvent can be used.

Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, and carboxylic acid. Glycol ethers such as bitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc.; acetic acid Esters of ethyl ester, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, etc.; esters of ethanol, propanol, ethylene glycol, propylene glycol, etc. Alcohols; aliphatic hydrocarbons such as octane and decane; petroleum-based solvents such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha, etc. Such organic solvents may be used alone or in a mixture of two or more.

A defoaming agent or leveling agent may be blended to prevent deterioration of surface smoothness and deterioration of interlayer insulation caused by holes or micropores. Defoaming agents (leveling agents) include polysilicone-based defoaming agents and non-polysilicone-based defoaming agents of foam-breaking polymer solutions. Commercially available polysilicone-based defoaming agents include BYK (Registered Trademark)-063, BYK (Registered Trademark)-065, BYK (Registered Trademark)-066N, BYK (Registered Trademark)-067A, BYK (Registered Trademark)-077 (the above are manufactured by BYK-Chemie Japan), KS -66 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

In addition, commercially available products of non-polysilicone-based defoaming agents include BYK (registered trademark)-054, BYK (registered trademark)-055, BYK (registered trademark)-057, BYK (registered trademark)-1790, BYK (Registered Trademark)-1791 (the above are manufactured by BYK-Chemie Japan), etc.

When a defoaming agent (leveling agent) is blended, the blending amount is 10 mass% or less, preferably 0.01 mass% or more, based on the total mass (solid content) of the thermosetting composition of the present invention. %the following.

A dispersant can be blended in order to improve the dispersibility and sedimentation properties of (B) alumina particles.

Commercially available dispersants include, 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-2000, DISPERBYK-2001, DISPERBYK-2009, DISPERBYK-2020, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2096, DISPERBYK-2150, BYK-P104, BYK-P104S, BYK-P105, K- 9076, BYK-9077, BYK-220S (the above are manufactured by BYK-Chemie Japan), DISPARLON 2150, DISPARLON 1210, DISPARLON KS-860, DISPARLON KS-873N, DISPARLON 7004, DISPARLON 1830, DISPARLON 1860, DISPARLON 1850 , DISPARLON DA -400N, DISPARLON PW-36, DISPARLON DA-703-50 (the above are manufactured by Kusumoto Chemical Co., Ltd.), FLORENE G-450, FLORENE G-600, FLORENE G-820, FLORENE G-700, FLORENE DOPA-44, FLORENE DOPA -17 (Made by Kyoeisha Chemical Co., Ltd.).

When blending a dispersant, the blending amount is 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass, based on 100 parts by mass (solid content) of the alumina particles (B).

As the coloring agent, conventionally known coloring agents such as red, blue, green, and yellow may be used, and any of pigments, dyes, and pigments may be used. Specific examples include coloring agents with a dye index (C.I.; published by The Society of Dyers and Colorists) number. However, from the viewpoint of reducing the environmental load and affecting the human body, a halogen-free coloring agent is preferable.

Examples of red colorants include monoazo series, disazo series, azo lake series, benzimidazolone series, perylene series, diketopyrrolopyrrole series, condensed azo series, anthraquinone series, and quinacridine Ketone series etc.

Phthalocyanine-based and anthraquinone-based blue colorants are known, and compounds classified as pigments are known as pigments. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

As green colorants, phthalocyanine-based, anthraquinone-based, and perylene-based colorants are similarly known. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Examples of yellow colorants include monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, and anthraquinone-based colorants.

In other aspects, for the purpose of adjusting the color tone, coloring agents such as purple, orange, brown, and black can also be added.

In addition, well-known and commonly used polymerization inhibitors, flame retardants, flame retardant auxiliaries, etc., such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, gallicol, phenothiazine, etc. can also be blended as necessary. Generally known and commonly used additives.

＜Coating base material＞ The coated base material of the present invention has a cured film of the thermosetting composition of the present invention.

The material of the high melting point base material which is coated with the curable composition of the present invention and has a melting point of 270° C. or higher is as described in the item of the thermosetting composition, and detailed description is omitted here.

In the present invention, the high melting point base material may be an injection molded body having a complex shape, or a wiring pattern (circuit) may be formed on its surface.

An example of a method for forming a wiring pattern on such an injection molded body is the LDS (Laser Direct Structuring) method. In the LDS method, a copper complex is first kneaded into a thermoplastic resin and injection molded, and then laser drawing is performed on the surface of a molded object containing the copper complex. By irradiating laser light, the copper complex will be metallized and exhibit the catalytic activity of electroless copper plating, and plating can be achieved in the laser-drawn part.

On the high-melting-point base material, the thermosetting composition of the present invention is adjusted to a viscosity suitable for the coating method using, for example, the above-mentioned organic solvent, and is coated by a dip coating method, a flow coating method, or a roll coating method. , rod coating method, screen printing method, curtain coating method, etc., and the organic solvent contained in the composition is volatilized and dried (pre-dried) at a temperature of about 60 to 130°C to form an insoluble Sticky paint film.

The volatilization drying after applying the thermosetting composition of the present invention can be carried out using a hot air circulation drying oven, an IR oven, a hot plate, a convection oven, etc. (use equipment equipped with an air heating type heat source using steam and dry it. The hot air in the machine is in counter-current contact and blown from the nozzle to the support).

By heating the coating film to a temperature of, for example, about 140 to 180° C. and thermally curing it, a coated base material according to the present invention in which a cured film is formed on a high melting point base material can be obtained.

Next, the covered base material with the circuit is exposed through a laser opening as a soldering surface, and the soldering pad is surface-treated with gold plating, and then the components are mounted by soldering.

Welding can be carried out by any method such as manual welding, flow soldering, reflow soldering, etc. For example, in the case of reflow soldering, it can be preheated at 100°C to 140°C for 1 to 4 hours, and then heated to 240°C or above. The solder is heated and melted by re-soldering by repeatedly heating at a temperature of 270°C for about 5 to 20 seconds several times (for example, 2 to 4 times).

After the reflow step, the parts are cooled and mounted to complete the three-dimensional circuit forming part (MID).

The coated base material of the present invention, that is, the coated base material having a cured film of the thermosetting composition of the present invention on a high melting point base material having a melting point of 270° C. or higher, has excellent heat resistance, rigidity, and adhesion to the base material. It has excellent adhesion and insulation properties, so it can be used in various applications, and there are no particular restrictions on the applicable objects. For example, it is possible to produce a coated substrate having an etching resist, a soldering resist, and a marking resist as a hardened film on a high-melting-point substrate formed by injection molding. Particularly from the perspective of improving weldability, it is possible to appropriately manufacture a substrate with the required high Heat-resistant solder resist serves as the coating base material for the cured film.

The following disclosed embodiments are specifically described for the present invention, but the present invention is not limited by these embodiments. In addition, unless otherwise specified below, "parts" means parts by mass. [Example]

<1. Preparation of thermosetting compositions of Examples 1 to 4 and Comparative Examples 1 to 4> 1. Preparation of thermosetting composition Each material was blended separately according to the ratio (unit: parts by mass) shown in Table 1, premixed with a mixer, and then kneaded with a three-roller mill to prepare a thermosetting composition.

The characteristic tests disclosed below were carried out for each of the thermosetting compositions described above. The results are shown in Table 1.

<2. Evaluation of the adhesion (checkerboard adhesion) of the coating film of the thermosetting composition> The thermosetting compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were printed on an LCP substrate (TECACOMP LCP LDS 4107 manufactured by Ensinger Co., Ltd.) by screen printing, and the dried coating film was made to be 30 μm. 60 minutes of heating to harden. In addition, the deflection temperature under load (DTUL) measured according to ASTM D648 (1.82MPa) of the above-mentioned LCP substrate is 274°C.

In accordance with JIS K 5600-5-6, the hardened coating film of the obtained hardened body was cut to produce 100 checkerboards (10×10) each with a vertical and horizontal width of 1 mm. Transparent adhesive tape (manufactured by Nichiban Co., Ltd., width: 18 mm) ) is completely attached to the checkerboard, immediately tear off the tape instantly while keeping one end of the tape at a right angle to the glass substrate, and check the state of the checkerboard. The evaluation criteria are as follows.

Adhesion (checkerboard adhesion) Category 0: The cut edges are completely smooth, and no grid is peeled off.

Category 1: The coating film at the cutting intersection is slightly peeled off. The proportion of cross-cut parts affected is definitely not higher than 5%.

Category 2: The coating peels off along the cut edges and/or at intersections. The affected proportion of the cross-cut part clearly exceeds 5% and is not higher than 15%.

Category 3: The coating film is severely peeled off partially or entirely along the cut edge and/or each part of the grid is partially or entirely peeled off. The affected proportion of the cross-cut part clearly exceeds 15% and is not higher than 35%.

Category 4: The coating film is severely peeled off partially or entirely along the cut edge and/or the grid is partially or entirely peeled off in several places. The proportion affected by the cross-cut part clearly exceeds 35% and is not higher than 65%.

Category 5: Severe peeling of Category 4 or above occurs.

<3. Evaluation of welding heat resistance of coating films of thermosetting compositions> The thermosetting compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were printed on an LCP substrate (TECACOMP LCP LDS 4107 manufactured by Ensinger Corporation) by screen printing, and the dried coating film was made to be 30 μm, and the temperature was increased by 150° C. 60 Minutes of heating to harden.

The obtained hardened coating film was coated with a rosin-based flux and immersed in a solder bath at 260° C. for 30 seconds. Then, it was washed with propylene glycol monomethyl ether acetate and dried, and then used a transparent adhesive tape (Nichiban Co., Ltd. (made, width: 18mm), perform a peeling test to evaluate whether there is peeling.

Welding heat resistance ○: No peeling. ×: There is peeling.

*1: Cresol novolak type epoxy resin, epoxy equivalent 209 to 219 (g/eq) (N-695: DIC Corporation) *2: Spherical alumina with an average particle diameter of approximately 8 μm (DAW-07: manufactured by Denka Corporation) *3: Spherical alumina with an average particle diameter of approximately 3 μm (DAW-03: manufactured by Denka Corporation) *4: Spherical alumina with an average particle diameter of approximately 0.3 μm (ASFP-20: manufactured by Denka Corporation) *5: Barium sulfate (B-30: manufactured by Sakai Chemical Industry Co., Ltd.) *6: Talc (LMS-200: manufactured by Fuji Talc Industry Co., Ltd.) *7: Polymer type, acrylic block copolymer with a PMMA (polymethyl methacrylate) ratio of 15 wt% (KURARITY (registered trademark) LA3320: manufactured by Kuraray Corporation) *8: Medium molecular type, acrylic block copolymer with a PMMA ratio of 20 wt% (KURARITY (registered trademark) LA2330: manufactured by Kuraray Corporation) *9: Low molecular type, acrylic block copolymer with a PMMA ratio of 20 wt% (KURARITY (registered trademark) LA2140: manufactured by Kuraray Corporation) *10: Medium molecular type, acrylic block copolymer with a PMMA ratio of 30 wt% (KURARITY (registered trademark) LA2250: manufactured by Kuraray Corporation) *11: Low molecular type, acrylic block copolymer with a PMMA ratio of 10 wt% (KURARITY (registered trademark) LA2114: manufactured by Kuraray Corporation) *12: Low molecular type, acrylic block copolymer with a PMMA ratio of 40 wt% (KURARITY (registered trademark) LA2270: manufactured by Kuraray Corporation) *13: Dicyanodiamide (DICY7: manufactured by Mitsubishi Chemical Corporation) *14: 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei Co., Ltd.) *15: Finely powdered melamine (Melamine: manufactured by Nissan Chemical Co., Ltd.) *16: Dipropylene glycol monoethyl ether *17: Silicone-based defoaming agent (KS-66: manufactured by Shin-Etsu Chemical Industry Co., Ltd.) *18: Non-silicon defoaming agent (BYK-1791: BYK-Chemie Japan Co., Ltd.) *19: Dispersant (BYK-111: BYK-Chemie Japan Co., Ltd.)

As shown in the examples of Table 1, when (B) alumina particles and (C) acrylic block copolymer are blended in which the mass percentage of the sum of X and X' is 12 mass % or more and 35 mass % or less, The cured film of the thermosetting composition of the present invention has good adhesion to the high melting point substrate and does not peel off. Similarly, when (B) alumina particles and (C) acrylic block copolymer in which the mass percentage of the sum of X and , the hardened coating did not crack.

On the other hand, as shown in Comparative Examples 1 and 2, if a block copolymer is blended in which the mass percentage of the sum of X and The adhesion of the cured film to the high-melting-point base material is reduced and peeling occurs.

In addition, as shown in Comparative Example 3, even if (C) acrylic block copolymer is blended in which the mass percentage of the sum of X and X' is 12 mass % or more and 35 mass % or less, (B) is not blended. When alumina particles are used as an inorganic filler, a cured film that is satisfactory in both welding heat resistance and adhesion cannot be obtained.

Claims (8)

A thermosetting composition for coating on a high-melting-point base material having a melting point of 270° C. or higher, characterized by containing: (A) a thermosetting component, (B) alumina particles , and (C) an acrylic block copolymer represented by the following formula (I) or the following formula (II), X-Y-X (I) or X-Y-X' (II) (in the formula, X and X' are The glass transition point Tg is a polymer block mainly composed of methacrylate units above 0°C, and Y is a polymer block mainly composed of acrylate units with a glass transition point Tg less than 0°C.) Compared with the aforementioned acrylic system The total mass of the block copolymer, the mass percentage of the sum of X and X' is in the range of 12 mass % or more and 35 mass % or less. The thermosetting composition according to claim 1, wherein (C) the acrylic block copolymer has a weight average molecular weight of 65,000 or more and 80,000 or less. The thermosetting composition of claim 1 or 2, wherein (C) the acrylic block copolymer is an acrylic block copolymer represented by the aforementioned formula (I). The thermosetting composition of claim 3, wherein in the aforementioned formula (I), X is a polymer block mainly composed of methyl methacrylate units, and Y is a polymer block mainly composed of n-butyl acrylate units. part. The thermosetting composition of claim 1 or 2, wherein (B) The amount of alumina particles is 40 mass% or more and 90 mass% or less based on the total mass of the thermosetting composition. The thermosetting composition of claim 1 or 2, wherein the amount of (C) acrylic block copolymer is 0.5 mass % or more and 20 mass % or less based on the total mass of the thermosetting composition. The thermosetting composition of claim 1 or 2, wherein the high melting point base material is selected from the group consisting of liquid crystal polymer, polyphenylene sulfide and polyether ether ketone. A coated base material, characterized by: a cured film having a thermosetting composition according to any one of claims 1 to 7.