# US 10,119,047 B2 · Thermosetting resin composition, and prepreg, insulating film with support, laminate plate, and printed wiring board, each obtained using same

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- Number: US 10,119,047 B2
- Document ID: US10119047B2
- Status: Granted
- Kind: B2
- Application number: 14/675,023
- Filed: 2015-03-31
- Published: 2015-07-23
- Granted: 2018-11-06
- Earliest claimed: 2009-03-27
- Assignees: Hitachi Chemical Company, Ltd.
- Applicants: Hitachi Chemical Company, Ltd.
- Inventors: Tomohiko Kotake; Shinji Tsuchikawa; Hiroyuki Izumi; Masato Miyatake; Shin Takanezawa; Hikari Murai; Tetsurou Irino
- Web page: https://patentgrep.com/patent/US10119047B2

## CPC

- C09D 179/085: {Unsaturated polyimide precursors}
- B32B 5/02: characterised by structural features of a {fibrous or filamentary} layer {(layer formed of metallic wires B32B15/02; layer formed of natural mineral fibres B32B19/02; layer formed of wood fibres B32B21/02)}
- B32B 5/24: one layer being a fibrous or filamentary layer
- B32B 15/14: next to a fibrous or filamentary layer
- B32B 27/06: as the main or only constituent of a layer, {which is} next to another layer of {the same or of} a {different material (next to a layer of a particular substance B32B9/045; next to a bituminous or tarry layer B32B11/046; next to a water setting substance layer B32B13/12; next to a metal layer B32B15/08; next to a glass layer B32B17/10; next to a layer formed of natural mineral fibres or particles B32B19/045; next to a wood layer B32B21/08; next to a cellulosic plastic layer B32B23/08; next to a natural or synthetic rubber layer B32B25/08)}
- B32B 27/18: characterised by the use of special additives
- B32B 27/20: using fillers, pigments, thixotroping agents
- B32B 27/281: {comprising polyimides}
- B32B 27/283: {comprising polysiloxanes}
- B32B 27/325: {comprising polycycloolefins}
- B32B 27/36: comprising polyesters
- B32B 27/38: comprising epoxy resins
- B32B 27/42: comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
- C08G 59/5073: {having two nitrogen atoms in the ring}
- C08J 5/244: {using glass fibres}
- C08J 5/249: {characterised by the additives used in the prepolymer mixture}
- C08L 63/00: Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L 79/085: {Unsaturated polyimide precursors}
- C09D 163/00: Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- H05K 1/0353: {consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement}
- B32B 2260/021: Fibrous or filamentary layer
- B32B 2260/023: Two or more layers
- B32B 2260/046: Synthetic resin
- B32B 2264/102: Oxide or hydroxide
- B32B 2307/306: Resistant to heat
- B32B 2307/50: having particular mechanical properties
- B32B 2307/536: Hardness
- B32B 2307/714: Inert, i.e. inert to chemical degradation, corrosion
- B32B 2307/7265: Non-permeable
- B32B 2457/08: PCBs, i.e. printed circuit boards
- Y10T 428/24802: Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T 428/249921: Web or sheet containing structurally defined element or component
- Y10T 428/31721: Of polyimide
- Y10T 442/2721: Nitrogen containing
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- H05K: PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

A thermosetting resin composition containing: (A) a resin composition having an unsaturated maleimide group, produced by reacting (a) a maleimide compound having at least two N-substituted maleimide groups per one molecule and (b) an amine compound having at least two primary amino groups per one molecule, in an organic solvent; (B) a thermosetting resin; and (C) a modified imidazole compound, such as an isocyanate-masked imidazole and an epoxy-masked imidazole, and a prepreg, an insulating film with a support, a laminate plate and a printed wiring board, each containing the same.

## Claims

### Claim 1

A thermosetting resin composition comprising:
(A) a resin composition having an unsaturated maleimide group, which is a reaction product produced by reacting (a) a maleimide compound having at least two N-substituted maleimide groups per one molecule and (b) an amine compound having at least two primary amino groups per one molecule, wherein in producing said reaction product, the maleimide compound (a) and the amine compound (b) are used in a ration that satisfies the equivalent ration (Ta/Tb) in a range of 1.0<Ta/Tb≤10.0, where (Ta/Tb) is the equivalent ratio of the equivalent (Ta) of the maleimide group in the maleimide compound (a) to the equivalent (Tb) of the —NH2 group in the amine compound (b);
(B) a thermosetting resin;
(C) a modified imidazole compound represented by any one of the following general formulae (I) and (II):
wherein R3, R4, R5 and R6 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having from 1 to 20 carbon atoms or a phenyl group;
and A represents an alkylene group or an aromatic hydrocarbon group,
wherein R3, R4, R5 and R6 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having from 1 to 20 carbon atoms or a phenyl group;
and B represents a single bond, an alkylene group, an alkylidene group, an ether group or a sulfonyl group; and
(D) an amine compound having an acidic substituent represented by the following general formula (IV):
wherein R1 each independently represent a hydroxyl group, a carboxyl group or a sulfonic acid group as the acidic substituent; R2 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having from 1 to 5 carbon atoms or a halogen atom; x represents an integer of from 1 to 5; and y represents an integer of from 0 to 4, provided that a sum of x and y is 5.

### Claim 2 (depends on 1)

The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition further comprises (E) an inorganic filler.

### Claim 3 (depends on 1)

The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition further comprises (F) a molybdenum compound.

### Claim 4 (depends on 1)

The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition further comprises (G) a phosphorus-containing compound that imparts flame retardancy.

### Claim 5 (depends on 1)

The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition further comprises (H) a compound that achieves chemical roughening.

### Claim 6 (depends on 1)

The thermosetting resin composition according to claim 1, wherein the thermosetting resin (B) is at least one selected from the group consisting of an epoxy resin, a phenol resin, an unsaturated imide resin, a cyanate resin, an isocyanate resin, a benzoxazine resin, an oxetane resin, an amino resin, an unsaturated polyester resin, an allyl resin, a dicyclopentadiene resin, a silicone resin, a triazine resin and a melamine resin.

### Claim 7 (depends on 2)

The thermosetting resin composition according to claim 2, wherein the inorganic filler (E) is fused spherical silica and/or a metal hydrate that has a thermal decomposition temperature of 300° C. or more.

### Claim 8 (depends on 1)

An insulating film with a support comprising a support having formed on a surface thereof a film containing the thermosetting resin composition according to claim 1 in a semi-cured state.

### Claim 9 (depends on 1)

A prepreg comprising the thermosetting resin composition according to claim 1 that is coated on a reinforcing substrate in a form of a fiber sheet, and is rendered into a B-stage.

### Claim 10 (depends on 8)

A laminate plate comprising at least one sheet of the insulating film with a support according to claim 8.

### Claim 11 (depends on 10)

A printed wiring board comprising the laminate plate according to claim 10.

### Claim 12 (depends on 9)

A laminate plate comprising at least one sheet of the prepreg according to claim 9.

### Claim 13 (depends on 12)

A printed wiring board comprising the laminate plate according to claim 12.

### Claim 14 (depends on 1)

A laminate plate comprising (i) at least one sheet of an insulating film with a support comprising a support having formed on a surface thereof a film containing the thermosetting resin composition according to claim 1 in a semi-cured state, and (ii) at least one sheet of a prepreg comprising said thermosetting resin composition that is coated on a reinforcing substrate in a form of a fiber sheet and is rendered into a B-stage.

### Claim 15 (depends on 14)

A printed wiring board comprising the laminate plate according to claim 14.

### Claim 16 (depends on 1)

The thermosetting resin composition according to claim 1, wherein said modified imidazole compound (C) is the compound represented by the general formula (I).

### Claim 17 (depends on 1)

The thermosetting resin composition according to claim 1, which contains 0.01 to 10 parts by mass of the modified imidazole compound (C) per 100 parts by mass of the thermosetting resin (B).

### Claim 18 (depends on 1)

The thermosetting resin composition according to claim 1, wherein said modified imidazole compound (C) is the compound represented by the general formula (II).

### Claim 19 (depends on 1)

A resin varnish comprising the thermosetting resin composition according to claim 1 and an organic solvent therefore.

### Claim 20 (depends on 1)

The thermosetting resin composition according to claim 1, wherein said reaction product has been produced by reacting said maleimide compound and said amine compound in an organic solvent.

### Claim 21 (depends on 1)

The thermosetting resin composition according to claim 1, wherein the amine compound (D) is at least one selected from the group consisting of m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline and 3,5-dicarboxyaniline.

### Claim 22 (depends on 1)

The thermosetting resin composition according to claim 1, wherein the resin composition having an unsaturated maleimide group (A) and the amine compound (D) are used in a ratio that satisfies the equivalent ratio (TA/TD) in a range of 1.0<(TA/TD)≤10.0, where (TA/TD) is the equivalent ratio of the equivalent (TA) of the maleimide group of the resin composition (A) to the equivalent (TD) of the —NH2 group in the amine compound (D).