CN101875825A - Halogen-free flame-retardant adhesive composition and flexible copper-clad plate using same - Google Patents

Abstract

The present invention discloses a halogen-free flame retardant adhesive composition, which includes the following components in parts by weight: 15 to 45 parts of halogen-free epoxy resin, 15 to 60 parts of thermoplastic resin and/or synthetic rubber, 0.1 to 8 parts of curing agent and 5 to 60 parts of nitrogen-containing flame retardant. The halogen-free flame retardant adhesive composition adopts nitrogen-containing flame retardant, reduces the use of phosphorus-containing flame retardant, and exhibits good flame retardancy, peel strength, electrical properties and welding heat resistance in the cured product, and does not contain harmful substances such as halogen and antimonide, and will not pollute the environment. The present invention also discloses a flexible copper clad laminate, which has an electrical insulating film, an adhesive layer and a copper foil, and the adhesive layer is prepared from the above-mentioned halogen-free flame retardant adhesive composition. The flame retardant grade of the flexible copper clad laminate reaches UL-94V0 level, and has good heat resistance, adhesion, solder resistance and other properties.

Description

Halogen-free flame-retardant adhesive composition and flexible copper-clad laminate using the composition

technical field

The invention relates to an adhesive composition, in particular to a halogen-free flame-retardant adhesive composition, and also relates to a flexible copper-clad laminate using the composition.

Background technique

In recent years, with the light weight, miniaturization and high density of electronic products, the demand for various printed circuit boards has increased, which also puts forward stricter requirements on the performance of copper clad laminate materials. At present, flame retardant copper clad laminate materials use a large amount of brominated epoxy resin and antimony compounds as flame retardants, but when electronic products made of such copper clad laminates are burned under abnormal conditions or waste products are burned, among them The bromine-containing substances and their synergistic flame retardant antimony trioxide will produce toxic gas dioxins and hydrogen halides, which are harmful to the environment and human health. The European Commission announced the "Waste Electrical and Electronic Equipment Directive" (referred to as "WEEEE Directive") and the "Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment Directive" (referred to as "RoHS Directive"), requiring that from July 1, 2006, Harmful substances such as lead, mercury, antimony, hexavalent chromium, polybrominated diphenyl ethers, and polybrominated biphenyls are prohibited from being used in electronic and electrical equipment newly put on the market. The implementation of the two directives of the European Union clearly puts forward the requirements of halogen-free and lead-free in the manufacturing process of printed circuit boards.

Halogen-free flame retardant copper clad laminate material is a flame retardant copper clad laminate that does not contain harmful substances such as halogen, lead, and antimony. At present, the main technical way to realize halogen-free flame retardancy of flexible copper clad laminates is to toughen phosphorus-containing epoxy resin with thermoplastic resin or rubber, and add other phosphorus-containing compounds and a certain amount of inorganic fillers such as aluminum hydroxide to assist flame retardancy, and use amino curing agent or phenolic resin as a curing agent for phosphorus-containing resins. However, due to the addition of a large amount of organophosphorus flame retardants and other inorganic fillers, on the one hand, there is a problem of uneven dispersion of fillers in the process of preparing the adhesive composition; Risk of insufficient adhesion of substrate to copper foil.

Contents of the invention

The first object of the present invention is to provide a halogen-free flame-retardant adhesive composition, which is halogen-free and has good flame retardancy, adhesion and mechanical properties.

The second object of the present invention is to provide a flexible copper-clad laminate using the above-mentioned halogen-free flame-retardant adhesive composition.

The first object of the present invention is achieved by the following technical measures: a halogen-free flame retardant adhesive composition, which includes the following components by weight:

Halogen-free epoxy resin 15-45 parts

Thermoplastic resin and/or synthetic rubber 15-60 parts

Curing agent 0.1～8 parts

Nitrogen-containing flame retardant 5-60 parts.

The halogen-free epoxy resin described in the present invention is an epoxy resin that does not contain halogen atoms in the molecular structure, for example, does not contain bromine, but contains at least two epoxy groups in each molecule. The present invention has no special restrictions on halogen-free epoxy resins, and various halogen-free epoxy resins sold on the market can be used, for example, phenol type, biphenyl type, bisphenol A epoxy resin or bisphenol F epoxy resin can be selected Resin and other types of halogen-free epoxy resins and their hydrides. Among them, bisphenol A epoxy resin and biphenyl type epoxy resin are preferable.

The halogen-free epoxy resin of the present invention may also be a halogen-free phosphorus-containing epoxy resin synthesized by using a reactive phosphorus compound to bond phosphorus atoms to the halogen-free epoxy resin, so The reactive phosphides mentioned above include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and compounds in which hydroquinone is used to replace the hydrogen atom bonded to the phosphorus atom of the compound. The halogen-free phosphorus-containing epoxy resin can adopt various halogen-free phosphorus-containing epoxy resins sold in the market.

The various halogen-free epoxy resins described in the present invention can be used alone, or two or more different halogen-free epoxy resins can be used in combination.

The thermoplastic resin described in the present invention can adopt the suitable thermoplastic resin of market sale, preferably can select polyester resin, acrylic resin, phenoxy resin and polyamide-imide resin etc. resin.

The various thermoplastic resins mentioned in the present invention can be used alone or in combination of two or more different thermoplastic resins.

The synthetic rubber of the present invention usually adopts acrylonitrile-butadiene copolymer, wherein preferably carboxyl-containing acrylonitrile-butadiene rubber, this type of carboxyl-containing acrylonitrile-butadiene rubber is acrylonitrile and butadiene copolymerization In the resulting rubber, carboxylation at the end of the copolymer molecule can be achieved by using a monomer containing a carboxyl group, such as methacrylic acid. Wherein the acrylonitrile content is between 5-60% by mass, preferably between 20-30% by mass. The described carboxyl-containing acrylonitrile-butadiene rubber can adopt related products sold in the market, such as: Nipol 1072 (Zeon Corporation), 1072CG (NantexIndustry Co., Ltd.) and high-purity, low-ionic impurity product XER- 32 (JSR Corporation). The present invention can also use high-purity carboxyl-containing acrylonitrile butadiene rubber, but the price is expensive, so although they can effectively improve the adhesion and anti-migration properties of the adhesive, it is difficult to use in large quantities.

The various synthetic rubbers mentioned in the present invention can be used alone, or in combination of two or more different synthetic rubbers.

The thermoplastic resin and synthetic rubber described in the present invention can be used in combination. At this time, the thermoplastic resin accounts for 10-30 parts by weight, and the synthetic rubber accounts for 10-30 parts by weight.

The present invention has no special restriction on the use of the curing agent, and any material commonly used as an epoxy resin curing agent can be used, wherein polyamine-based curing agents and/or acid anhydride-based curing agents are preferred. The polyamine-based curing agents that can be selected include diaminodiphenylsulfone, phenylenediamine, and diaminodiphenylmethane, etc.; the anhydride-based curing agents that can be selected include phthalic anhydride, pyromellitic anhydride, etc. , and hexahydrophthalic anhydride, etc. Various curing agents described in the present invention may be used alone or in combination of two or more.

The nitrogen-containing flame retardant of the present invention requires that the nitrogen content is usually within the range of 15-30% by mass, preferably within the range of 15-25% by mass. Phosphorus-free nitrogen-containing flame retardants such as melamine and melamine urate can be selected. agent. The nitrogen-containing flame retardant can also be selected from nitrogen-containing polyphosphate compounds. On the one hand, this type of compound can provide the cured product with superior flame retardancy without losing the welding heat resistance under normal conditions of the cured product. On the one hand, it can improve the anti-migration performance of the cured product without losing the soldering heat resistance under moisture absorption conditions, and does not contain halogen atoms. The nitrogen-containing polyphosphate compound is preferably melamine polyphosphate, or piperazine polyphosphate, or a mixture of melamine polyphosphate and piperazine polyphosphate. The melamine polyphosphate may preferably be melamine pyrophosphate, melamine triphosphate, melamine pentaphosphate or melamine salt of pentaerythritol acid phosphate. The piperazine polyphosphate can be selected from piperazine pyrophosphate, piperazine triphosphate, piperazine pentaphosphate or 2,4-diamino-6-diethoxyphosphoryl-1,3,5-tri oxazine (DAPT), etc. Wherein the nitrogen-containing polyphosphoric acid compound is more preferably melamine pyrophosphate, piperazine pyrophosphate or a mixture of the two. Various flame retardants in the present invention can be used alone or in combination of two or more compounds.

The invention can be improved as follows: adding inorganic fillers to the halogen-free flame-retardant adhesive composition. The present invention has no special restriction on the type of inorganic filler used, and any filler used in conventional flexible copper-clad laminate materials can be used. From the consideration of the role of flame retardant auxiliary agent, metal oxides such as aluminum hydroxide, magnesium hydroxide, talc, titanium dioxide, silicon dioxide, calcium carbonate, zeolite, boron nitride, aluminum nitride, clay and One or a mixture of mica. The present invention has no special limitation on the amount of the above-mentioned inorganic fillers, but the amount is preferably 5-60 parts by weight, more preferably 20-40 parts by weight.

The present invention can also be improved as follows: 0.1-1 weight part of curing agent accelerator is added to the halogen-free flame-retardant adhesive composition to accelerate the reaction between the halogen-free epoxy resin and the curing agent. The curing agent accelerator described in the present invention can adopt the existing curing agent accelerator in the prior art, wherein preferably one or both in imidazole compound, triorganophosphine compound, quaternary ammonium salt and fluoborate etc. Mix the above. The imidazole compound can preferably adopt 2-methylimidazole, 1-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole (2E4MZ), 1-cyanoethyl -2-Ethyl-4-methylimidazole (2E4MZ-CN), 2-undecylimidazole (C11Z), 1-cyanoethyl-2-undecylimidazole (C11Z-CN) and 2-decylimidazole Heptaalkylimidazole (C17Z), the above imidazole compounds can be used alone or in combination of two or more. The triorganophosphine compound may preferably be triphenylphosphine or tributylphosphine. Described quaternary ammonium salt can preferably adopt the three (diethylacetic acid) salt of 2,4,6-tris (dimethylaminomethyl) phenol or 2,4,6-tris (dimethylaminomethyl) ) Trioleate of phenol, etc. The fluoroborate can be selected from complexes of boron trifluoride and monoethylamine, complexes of boron trifluoride and n-butylamine, complexes of boron trifluoride and benzylamine, and boron trifluoride One or a mixture of two or more of complexes with dimethylaniline, etc.

The present invention can also be further improved: a phosphorus-containing flame retardant is added to the halogen-free flame-retardant adhesive composition, and the phosphorus-containing flame retardant can be used as a synergistic flame retardant of the nitrogen-containing flame retardant, and can be used Organic phosphorus compounds, such as phenolic azophosphorus oligomers, etc.; or organic phosphonates, such as dimethyl methyl phosphonate, or diethyl ethyl phosphonate, etc., or phosphinates, such as alkali Metal phosphonite: sodium phosphonite, potassium phosphonite, etc. The added amount of the phosphorus-containing flame retardant is 5-15 parts by weight.

In the present invention, an appropriate amount of antioxidant can also be added, and the added amount is 0.1-3 parts by weight. The antioxidant is preferably a polybasic hindered phenolic antioxidant, such as antioxidant 1010, phosphite antioxidant 168, or phosphite antioxidant 626, or a mixture thereof.

Using the above-mentioned halogen-free flame-retardant adhesive composition to prepare the adhesive method: weigh the halogen-free epoxy resin, thermoplastic resin and/or synthetic rubber, curing agent and nitrogen-containing flame retardant according to the amount of the above-mentioned components, and place In grinding equipment such as a sand mill, add an organic solvent for mixing and grinding, and then send it to a high-shear stirring and dispersing equipment to mix evenly. According to actual needs, curing agent accelerators, inorganic fillers and phosphorus-containing flame retardants can also be added for thorough mixing. The solid content of the finally obtained adhesive is preferably between 30-40% by mass, which can obtain proper viscosity, provide good processability, and ensure no apparent defects in the coating process.

Above-mentioned organic solvent can be acetone, butanone, cyclohexanone, toluene, xylene, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, ethyl One or more of glycol methyl ether and propylene glycol methyl ether.

The second object of the present invention is achieved through the following technical solutions: a flexible copper-clad laminate, which has an electrical insulation film, an adhesive layer and a copper foil, the adhesive layer is made of the above-mentioned halogen-free flame-retardant adhesive composition Prepared.

The electrical insulation film is polyimide (PI) film or polyethylene terephthalate (PET) film, with a thickness of 5-100 μm.

The copper foil can be electrolytic copper foil or rolled copper foil, and the thickness can be in the range of 1-100 μm.

The dry thickness of the layer formed by the halogen-free flame-retardant adhesive composition may be in the range of 5-45 μm.

The production of the flexible copper clad laminate of the present invention comprises the following steps:

(1) Weigh the components of the above-mentioned halogen-free flame-retardant adhesive composition in proportion, place them in a grinding equipment, add an organic solvent for mixing and grinding, and then send them to a high-shear stirring and dispersing equipment to mix evenly to form a halogen-free flame-retardant adhesive composition. Burn the liquid dispersion of the adhesive composition, and then use the coating equipment to coat the dispersion on one side or both sides on the electrical insulation film, and the coating thickness is 5-45um;

(2) Pass the electrical insulating film coated with the adhesive composition dispersion in step (1) through a drying oven to remove the organic solvent and dry the adhesive composition so that it forms a semi-cured halogen-free flame-retardant adhesive agent composition layer, the drying temperature is 80-170°C, and the heating time is 2-10 minutes;

(3) At a temperature of 80-120°C, roll and apply the electrical insulation film with adhesive layer and copper foil in step (2), and then apply the semi-cured single-sided or double-sided flexible copper clad laminate Curing, the post-curing temperature is 120-180°C.

Compared with the prior art, the present invention has the following beneficial effects:

(1) The use of nitrogen-containing flame retardants in the halogen-free flame-retardant adhesive composition provided by the present invention reduces the use of phosphorus-containing flame retardants, and the cured product exhibits good flame retardancy, peel strength, electrical Performance and welding heat resistance, and does not contain harmful elements such as halogens and antimonides, and will not pollute the environment.

(2) The flexible copper clad laminate prepared using the halogen-free flame retardant adhesive composition of the present invention has the following advantages:

1) The flame retardant grade reaches UL-94V0 grade.

2) It has good heat resistance and adhesion, and the peel strength of MOT test (150°C, 10 days) is still 0.49Kgf/cm.

3) Solder resistance, immersion in tin at 300°C for 1 min without delamination or blistering.

Detailed ways

The present invention will be further described below through embodiment. The amounts and proportions of raw materials involved in each embodiment are mass proportions, unless otherwise specified.

The selection of each raw material is detailed as follows:

1. Halogen-free epoxy resin

Adopt various halogen-free epoxy resins sold on the market, for example: phenol type epoxy resin has: trade name is XD-1000 (Nippon Kayaku Co., Ltd. epoxy equivalent: 246g/eq). Biphenyl type epoxy resin has: NC-3000 (Nippon Kayaku Co., Ltd epoxy equivalent: 280g/eq). Bisphenol A epoxy resins include: GELR128E (Hongchang Electronic Materials Co., Ltd., epoxy equivalent: 185g/eq), KET4131A70 (KOLON, epoxy equivalent: 215.5g/eq). Bisphenol F epoxy resin has: NC-2000-L (Nippon Kayaku Co., Ltd epoxy equivalent: 280g/eq).

Phosphorus-containing epoxy resins can also be used effectively to form a halogen-free flame-retardant adhesive composition, and the phosphorus-containing epoxy resins can use various halogen-free epoxy resins sold on the market, including 9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and compounds wherein the hydrogen atom bonded to the phosphorus atom of the compound is replaced by hydroquinone. The example of described phosphorus-containing epoxy resin has: ULE241P-K-70 (Lianzhong Technology Co., Ltd., epoxy equivalent: 416g/eq, phosphorus content: 2.4 quality %), STRUKTOL VP3742 (German Melchers, Epoxy equivalent: 370 g/eq, phosphorus content: 4.5 mass %) PN-106 (Jinyi Chemical Industry, epoxy equivalent: 375 g/eq, phosphorus content: 2.9 mass %).

The above halogen-free epoxy resins may be used alone, or in combination of two or more different resins.

2. Thermoplastic resin

Various thermoplastic resins available in the market can be used, and suitable thermoplastic resins include polyester resin, acrylic resin, phenoxy resin and polyamideimide resin. The options are PPO*MX-90 (phenoxy resin, SABICINNOVATIVE PLASTICS), Kayaflex series (polyamideimide resin, Nippon Kayaku Co., Ltd.) and KS series (acrylic resin containing epoxy group, Hitachi Chemical Co., Ltd.).

3. Synthetic rubber

The synthetic rubber can be carboxyl-containing acrylonitrile-butadiene rubber. This type of carboxyl-containing nitrile rubber is a rubber produced by the copolymerization of acrylonitrile and butadiene, and an acrylonitrile-butadiene copolymer with an acrylonitrile content of 5-60% by mass is selected. Acrylonitrile-butadiene copolymers having an acrylonitrile content between 20 and 30% by mass are preferred. Specific examples of these commercially available carboxyl group-containing rubbers are Nipol 1072 (Zeon Corporation), 1072CG (Nantex Industry Co., Ltd.) and a high-purity, low-ionic-impurity product XER-32 (JSR Corporation). The present invention can also use high-purity carboxyl-containing acrylonitrile butadiene rubber, but the price is expensive, so although they can effectively improve the adhesion and anti-migration properties of the adhesive, it is difficult to use in large quantities.

The thermoplastic resin and the synthetic rubber may be used alone or in combination. A combination of two or more thermoplastic resins or two or more synthetic rubbers may also be used.

4. Curing agent

The present invention has no special restriction on the use of the curing agent, and any materials commonly used as curing agents for epoxy resins can be used, preferably polyamine-based curing agents and acid anhydride-based curing agents. Among them, polyamine-based curing agents can be selected from diaminodiphenylsulfone, phenylenediamine, and diaminodiphenylmethane. The curing agent based on acid anhydride can be selected from phthalic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride and the like. Each of the above-mentioned curing agents can be used alone or in combination of two or more.

5. Curing agent accelerator

The specific example of the curing agent accelerator that can be used can be selected imidazole compound, as 2-methylimidazole, 1-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole ( 2E4MZ), 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN), 2-undecylimidazole (C11Z), 1-cyanoethyl-2-undecylimidazole ( C11Z-CN) and 2-heptadecyl imidazole (C17Z); triorganophosphine compounds such as triphenylphosphine, tributylphosphine, etc. can also be selected; quaternary ammonium salts or fluoroborates can also be selected.

6. Nitrogen-containing flame retardants

Various existing nitrogen-containing flame retardants can be used, among which nitrogen-containing flame retardants with a nitrogen content in the range of 15-30 mass % are selected, preferably nitrogen-containing flame retardants with a nitrogen content in the range of 15-25 mass %. Nitrogen-containing polyphosphate compounds such as melamine polyphosphate (MPP), piperazine polyphosphate or mixtures thereof are preferred in the present invention. Specific examples are melamine pyrophosphate, melamine triphosphate, melamine pentaphosphate, piperazine pyrophosphate, piperazine triphosphate and piperazine pentaphosphate.

7. Phosphorus-containing flame retardants

Phosphorus-containing flame retardants can choose to use organic phosphorus compounds, such as phenolic azophosphorus oligomer (FP110), etc.; organic phosphonates, such as dimethyl methyl phosphonate, diethyl ethyl phosphonate, etc.; and Phosphonites, such as alkali metal phosphonites: sodium phosphonite, potassium phosphonite, etc.

8. Inorganic filler

The present invention has no special restriction on inorganic fillers, and any fillers used in conventional flexible copper-clad laminate materials can be used. In particular, metal oxides such as aluminum hydroxide, magnesium hydroxide, talc, titania silica, calcium carbonate, zeolite, boron nitride, aluminum nitride, One or more mixtures of clay and mica.

9. Organic solvents

The organic solvent used when the present invention is prepared into adhesive can be acetone, butanone, cyclohexanone, toluene, xylene, N, N-dimethylacetamide, N, N-dimethylformamide, N- One or more of methyl-2-pyrrolidone, ethylene glycol methyl ether, and propylene glycol methyl ether. The solid content of the prepared composition is preferably 30-40% by mass, which can obtain proper viscosity, provide good processability, and ensure no apparent defects in the coating process.

10. Antioxidant

The antioxidant used in the present invention is a multivariate hindered phenolic antioxidant, such as antioxidant 1010, phosphite antioxidant 168, 626, etc. or a mixture thereof

11. Electrical insulating film

The present invention has no particular limitation on the electrical insulation film used for flexible copper clad laminates, and any film material commonly used for flexible copper clad laminates can be used. Examples of suitable electrically insulating films are polyimide films, polyethylene terephthalate films, polyether ether ketone films, and the like. From the viewpoint of the heat resistance, dimensional stability and mechanical properties of the produced copper clad laminate, a polyimide film is preferred, and its thickness is preferably 10-100 μm.

Describe the present invention in more detail as following examples, but the present invention is by no means limited by following examples:

Example 1:

Halogen-free epoxy resin STRUKTOLVP 3742 (German Melchers, epoxy equivalent: 370g/eq, phosphorus content: 4.5% by mass) 8 parts by weight, ULE241P-K-70 (Lianzhong Technology Co., Ltd., epoxy equivalent: 416g/eq, phosphorus content: 2.4% by mass) 16 parts by weight, XD-1000 (Nippon Kayaku Co., Ltd epoxy equivalent: 246g/eq) 8 parts by weight, GELR128E (Hongchang Electronic Materials Co., Ltd., epoxy equivalent: 185g/eq) 2 parts by weight; 40 parts by weight of synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile content 27% by mass); 2 parts by weight of diaminodiphenyl sulfone; 1-cyanoethyl-2-ethyl- 0.3 parts by weight of 4-methylimidazole (2E4MZ-CN); 43 parts by weight of nitrogen-containing flame retardant melamine polyphosphate (MPP, nitrogen content 18%); aluminum hydroxide (average particle diameter 0.8-1.2 μm, purity 99 % or more) 27 parts by weight; antioxidant 1010 (CIBA GEIGY Co., Ltd.) 1.0 parts by weight. Put the above components in a sand mill, add methyl ethyl ketone solvent, adjust the solid content of the composition to 35%, and then mix and grind to prepare a liquid dispersion of the halogen-free flame-retardant adhesive composition.

The liquid dispersion of the halogen-free flame-retardant adhesive composition was coated on a polyimide film with a thickness of 12.5 μm by a coating machine, and the coating thickness was 13 μm, and then the coated coating was applied in a forced-air oven. The layer was dried at 150° C. for 5 minutes, so that the coating of the halogen-free flame-retardant adhesive composition was transformed into a semi-cured adhesive layer. The surface of the polyimide film with the adhesive layer and one surface of the electrolytic copper foil (thickness 18 μm) were bonded together by thermocompression bonding at 120°C using a roll laminator, and then the laminate Put it into an oven to heat up and cure at 60-180°C to make a flexible copper clad laminate.

Example 2:

Halogen-free epoxy resin STRUKTOLVP 3742 (German Melchers, epoxy equivalent: 370g/eq, phosphorus content: 4.5% by mass) 10 parts by weight, ULE241P-K-70 (Lianzhong Technology Co., Ltd., epoxy equivalent: 416g/eq, phosphorus content: 2.4% by mass) 21 parts by weight, XD-1000 (Nippon Kayaku Co., Ltd epoxy equivalent: 246g/eq) 10 parts by weight, GELR128E (Hongchang Electronic Materials Co., Ltd., epoxy equivalent: 185g/eq) 2 parts by weight; 42 parts by weight of synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile content 27% by mass); 8 parts by weight of diaminodiphenyl sulfone; 1-cyanoethyl-2-ethyl- 0.3 parts by weight of 4-methylimidazole (2E4MZ-CN); 46 parts by weight of nitrogen-containing flame retardant melamine polyphosphate (MPP, nitrogen content 18%); aluminum hydroxide (average particle diameter 0.8-1.2 μm, purity 99 % or more) 27 parts by weight; antioxidant 1010 (CIBA GEIGY Co., Ltd.) 1.0 parts by weight. Put the above components in a sand mill, add butanone solvent, adjust the solid content of the composition to 30%, and then mix and grind to prepare a liquid dispersion of the halogen-free flame-retardant adhesive composition.

The liquid dispersion of the halogen-free flame-retardant adhesive composition was coated on a polyimide film with a thickness of 12.5 μm by a coating machine, and the coating thickness was 13 μm, and then the coated coating was applied in a forced-air oven. The layer was dried at 150° C. for 5 minutes, so that the coating of the halogen-free flame-retardant adhesive composition was transformed into a semi-cured adhesive layer. The surface of the polyimide film with the adhesive layer and one surface of the rolled copper foil (thickness 18 μm) were bonded together by thermocompression bonding at 120°C using a roll laminator, and then the laminate Put it into an oven to heat up and cure at 60-180°C to make a flexible copper clad laminate.

Example 3:

Halogen-free epoxy resin PN-106 (Jinyi Chemical, epoxy equivalent: 340g/eq, phosphorus content: 2.6 mass %) 4 parts by weight, STRUKTOL VP3742 (Germany Melchers, epoxy equivalent: 370g/eq, phosphorus Content: 4.5% by mass) 10 parts by weight, ULE241P-K-70 (Hongchang Electronic Materials Co., Ltd., epoxy equivalent: 416g/eq, phosphorus content: 2.4% by mass) 21 parts by weight, KET4131A70 (KOLON, epoxy equivalent: 215.5g/eq) 5 parts by weight; synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile content 27% by mass) 18 parts by weight; thermoplastic resin phenoxy resin (PPO*MX-90, SABIC INNOVATIVE PLASTICS) 25 parts by weight 4.6 parts by weight of diaminodiphenyl sulfone; 0.4 parts by weight of 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN); nitrogen-containing flame retardant melamine polyphosphate (MPP, nitrogen-containing Amount 18%) 60 parts by weight. Put the above components in a sand mill, add butanone solvent, adjust the solid content of the composition to 38%, and then mix and grind to prepare a liquid dispersion of the halogen-free flame-retardant adhesive composition.

The liquid dispersion of the halogen-free flame-retardant adhesive composition was coated on a polyimide film with a thickness of 12.5 μm by a coating machine, and the coating thickness was 13 μm, and then the coated coating was applied in a forced-air oven. The layer was dried at 150° C. for 5 minutes, so that the coating of the halogen-free flame-retardant adhesive composition was transformed into a semi-cured adhesive layer. The surface of the polyimide film with the adhesive layer and one surface of the electrolytic copper foil (thickness 18 μm) were bonded together by thermocompression bonding at 120°C using a roll laminator, and then the laminate Put it into an oven to heat up and cure at 60-180°C to make a flexible copper clad laminate.

Example 4:

Halogen-free epoxy resin PN-106 (Jinyi Chemical, epoxy equivalent: 340g/eq, phosphorus content: 2.6 mass %) 4 parts by weight, STRUKTOL VP3742 (Germany Melchers, epoxy equivalent: 370g/eq, phosphorus Content: 4.5% by mass) 10 parts by weight, ULE241P-K-70 (Hongchang Electronic Materials Co., Ltd., epoxy equivalent: 416g/eq, phosphorus content: 2.4% by mass) 21 parts by weight, KET4131A70 (KOLON, epoxy equivalent: 215.5g/eq) 5 parts by weight; synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile content 27% by mass) 30 parts by weight; thermoplastic resin phenoxy resin (PPO*MX-90, SABIC INNOVATIVE PLASTICS) 10 parts by weight 5 parts by weight of diaminodiphenyl sulfone; 0.3 parts by weight of 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN); nitrogen-containing flame retardant MPP46 parts by weight; aluminum hydroxide (average Particle size 0.8-1.2 μm, purity above 99%) 27 parts by weight; Antioxidant 1010 (CIBA GEIGY Co., Ltd.) 1.0 parts by weight. Put the above components in a sand mill, add butanone solvent, adjust the solid content of the composition to 40%, and then mix and grind to prepare a liquid dispersion of the halogen-free flame-retardant adhesive composition.

The dispersion was coated on a polyimide film with a thickness of 12.5 μm with a coating machine, and the coating thickness was 13 μm, and then the coated coating was dried at 150° C. for 5 minutes in a forced-air oven, thereby The halogen-free flame-retardant adhesive composition coating is transformed into a semi-cured adhesive layer. The surface of the polyimide film with the adhesive layer and one surface of the electrolytic copper foil (thickness 18 μm) were bonded together by thermocompression bonding at 120°C using a roll laminator, and then the laminate Put it into an oven to heat up and cure at 60-180°C to make a flexible copper clad laminate.

Example 5:

Halogen-free epoxy resin STRUKTOL VP3742 (Melchers, Germany, epoxy equivalent: 370g/eq, phosphorus content: 4.5% by mass) 10 parts by weight, ULE241P-K-70 (Lianzhong Technology Co., Ltd., epoxy equivalent: 416g/eq, phosphorus content: 2.4% by mass) 21 parts by weight, XD-1000 (Nippon Kayaku Co., Ltd epoxy equivalent: 246g/eq) 10 parts by weight, GELR128E (Hongchang Electronic Materials Co., Ltd., epoxy equivalent: 185g/eq) 2 parts by weight; synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile content 27% by mass) 46 parts by weight; diaminodiphenylsulfone 6 parts by weight; 1-cyanoethyl-2-ethyl- 0.3 parts by weight of 4-methylimidazole (2E4MZ-CN); 35 parts by weight of nitrogen-containing flame retardant MPP; 9 parts by weight of OP935 (Clariant Produkte GmbH, with an average particle size of 1-5 μm); aluminum hydroxide (average particle size 0.8 -1.2 μm, purity more than 99%) 27 parts by weight; Antioxidant 1010 (CIBA GEIGY Co., Ltd.) 1.0 parts by weight. Put the above components in a sand mill, add methyl ethyl ketone solvent, adjust the solid content of the composition to 35%, and then mix and grind to prepare a liquid dispersion of the halogen-free flame-retardant adhesive composition.

The dispersion was coated on a polyimide film with a thickness of 12.5 μm with a coating machine, and the coating thickness was 13 μm, and then the coated coating was dried at 150° C. for 5 minutes in a forced-air oven, thereby The halogen-free flame-retardant adhesive composition coating is transformed into a semi-cured adhesive layer. The surface of the polyimide film with the adhesive layer and one surface of the electrolytic copper foil (thickness 18 μm) were bonded together by thermocompression bonding at 120°C using a roll laminator, and then the laminate Put it into an oven to heat up and cure at 60-180°C to make a flexible copper clad laminate.

Comparative example 1:

Halogen-free epoxy resin STRUKTOLVP 3742 (Melchers, Germany, epoxy equivalent: 370ag/eq, phosphorus content: 4.5% by mass) 10 parts by weight, ULE241P-K-70 (Lianzhong Technology Co., Ltd., epoxy equivalent: 416g/eq, phosphorus content: 2.4% by mass) 21 parts by weight, XD-1000 (Nippon Kayaku Co., Ltd epoxy equivalent: 246g/eq) 10 parts by weight, synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile 40 parts by weight of content 27% by mass; 5.5 parts by weight of diaminodiphenyl sulfone; 0.3 parts by weight of 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN); nitrogen-containing flame retardant MPP 18 Parts by weight; 18 parts by weight of phosphorus-containing flame retardant OP935 (Clariant Produkte GmbH, with an average particle diameter of 1-5 μm); 24 parts by weight of aluminum hydroxide (average particle diameter of 0.8-1.2 μm, with a purity of more than 99%); antioxidant 1010 (CIBA GEIGY Co., Ltd.) 0.9 parts by weight. Put the above components in a sand mill, add methyl ethyl ketone solvent, adjust the solid content of the composition to 35%, and then mix and grind to prepare a liquid dispersion of the halogen-free flame-retardant adhesive composition.

The dispersion was coated on a polyimide film with a thickness of 12.5 μm with a coating machine, and the coating thickness was 13 μm, and then the coated coating was dried at 150° C. for 5 minutes in a forced-air oven, thereby The halogen-free flame-retardant adhesive composition coating is transformed into a semi-cured adhesive layer. The surface of the polyimide film with the adhesive layer and one surface of the electrolytic copper foil (thickness 18 μm) were bonded together by thermocompression bonding at 120°C using a roll laminator, and then the laminate Put it into an oven to heat up and cure at 60-180°C to make a flexible copper clad laminate.

Comparative example 2:

Halogen-free epoxy resin PN-106 (Jinyi Chemical, epoxy equivalent: 340g/eq, phosphorus content: 2.6% by mass) 4 parts by weight, ULE241P-K-70 (Hongchang Electronic Materials Co., Ltd., epoxy equivalent: 416g /eq, phosphorus content: 2.4 mass %) 20 parts by weight, 901 (Hongchang Electronic Materials Co., Ltd., epoxy equivalent: 215.5g/eq) 5 parts by weight; GELR128E (Hongchang Electronic Materials Co., Ltd., epoxy equivalent: 185g /eq) 2 parts by weight; 40 parts by weight of synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile content 27% by mass); 4.6 parts by weight of diaminodiphenyl sulfone; 1-cyanoethyl-2-ethyl-4 - 0.4 parts by weight of methylimidazole (2E4MZ-CN); 60 parts by weight of phosphorus-containing flame retardant OP93560. Put the above components in a sand mill, add butanone solvent, adjust the solid content of the composition to 38%, and then mix and grind to prepare a liquid dispersion of the halogen-free flame-retardant adhesive composition.

The dispersion was coated on a polyimide film with a thickness of 12.5 μm with a coating machine, and the coating thickness was 13 μm, and then the coated coating was dried at 150° C. for 5 minutes in a forced-air oven, thereby The halogen-free flame-retardant adhesive composition coating is transformed into a semi-cured adhesive layer. The surface of the polyimide film with the adhesive layer and one surface of the electrolytic copper foil (thickness 18 μm) were bonded together by thermocompression bonding at 120°C using a roll laminator, and then the laminate Put it into an oven to heat up and cure at 60-180°C to make a flexible copper clad laminate.

The performances of the flexible copper-clad laminates obtained in the above-mentioned examples and comparative examples are measured and compared as follows, and the obtained results are shown in Table 1:

1. Measurement method:

Flame retardant:

Flame samples were prepared by etching through the flexible copper clad laminate to remove all copper foil. Then the flame retardancy of the samples was tested according to the UL94-V0 vertical burning method. If the sample meets the flame retardant requirements of UL94-V0, the sample is evaluated as "good" and represented by the symbol "○", otherwise, it is evaluated as "poor" and represented by the symbol "×".

Soldering heat resistance:

The soldering heat resistance of the test material is tested in accordance with IPC-6502.4.13, which is measured by cutting 25 cm2 of the flexible CCL material to prepare test samples, and then immersing these test samples in a tin melting bath at 300°C for 1 min. No air bubbles or delamination occurred in the test sample, and it was judged as "OK".

Peel strength:

According to IPC-6502.4.9 method, test the peel strength of copper foil. The specific method is: form a circuit with a width of 1mm on the flexible copper clad board by exposure etching, and then measure and peel off the copper foil circuit at a speed of 50mm/min in the direction of 90 degrees to the laminate material at a temperature of 25°C The minimum force required and this measurement is taken as the peel strength.

Plating connection strength and delamination test (MOT test)

Test according to ASTM D5423 (1993), put the etched 1mm line in an air circulation furnace at 150°C for 240 hours, then cool to room temperature to test the adhesion between copper foil and the substrate. UL79626C requires peel strength greater than 0.35Kgf/cm.

Table I

As can be seen from Table 1, the compositions prepared in Examples 1 to 5 meet the requirements of the present invention, and the flexible copper-clad laminate material produced by the nitrogen-containing flame retardant resin composition shows good peel strength (normal state and MOT), welding Heat resistance and flame retardancy, as well as being halogen-free, have important industrial application prospects. And in comparative example 1 and 2, use phosphorus-containing flame retardant to replace nitrogen-containing flame retardant, and when comparing with the flexible copper clad laminate meeting the requirements of the present invention, the flexible copper clad laminate material of its gained is in flame retardancy and peel strength ( MOT) and other poor performance.

The present invention may be embodied in other specific forms without departing from the spirit or main characteristics of the invention. The above-mentioned embodiments of the present invention can only be considered as an illustration of the present invention rather than a limitation, so any minor modifications, equivalent changes and modifications made to the above examples according to the essential technology of the present invention or composition components or content are all valid. It belongs to the scope of the technical solutions of the present invention.

Claims (10)

1. a halogen-free flame-retardant adhesive composition is characterized in that, it comprises the component of following weight part:

15～45 parts of halogen Resins, epoxy

15～60 parts of thermoplastic resin and/or synthetic rubber

0.1～8 part in solidifying agent

Contain 5～60 parts of nitrogen combustion inhibitors.

2. halogen-free flame-retardant adhesive composition according to claim 1, it is characterized in that, when described thermoplastic resin and synthetic rubber mixing use, it is 10-30 part that described thermoplastic resin accounts for weight part, and it is 10-30 part that described synthetic rubber accounts for weight part.

3. halogen-free flame-retardant adhesive composition according to claim 1 and 2, it is characterized in that described halogen Resins, epoxy is the halogen Resins, epoxy of phenol type, biphenyl type, bisphenol A epoxide resin or bisphenol F epoxy resin type and one or more the combination in their hydride and the halogen phosphorous epoxy resin; Described thermoplastic resin is one or more the combination in vibrin, acrylic resin, phenoxy resin and the polyamide-imide resin; Described synthetic rubber is the acrylonitrile butadiene copolymer of acrylonitrile content between 5-60 quality %; Described solidifying agent adopts based on the solidifying agent of polyamines and/or the solidifying agent of acid anhydride-based; The described nitrogen combustion inhibitor requirement nitrogen content that contains is in 15-30 quality % scope.

4. halogen-free flame-retardant adhesive composition according to claim 3 is characterized in that, the combination of one or more among described synthetic rubber employing Nipol 1072,1072CG and the XER-32; Described solidifying agent based on polyamines adopts one or more the combination in diaminodiphenylsulfone(DDS), phenylenediamine and the diaminodiphenyl-methane; One or more combination in solidifying agent employing Tetra hydro Phthalic anhydride, pyromellitic acid acid anhydride and the hexahydrophthalic anhydride of described acid anhydride-based; The described nitrogen combustion inhibitor that contains adopts trimeric cyanamide, trimeric cyanamide urate, trimeric cyanamide polyphosphate, piperazine polyphosphate, melamine pyrophosphate, trimeric cyanamide triphosphate, trimeric cyanamide pentaphosphate, the melamine salt of tetramethylolmethane phosphate ester acid, piperazine pyrophosphate salt, piperazine triphosphate, piperazine pentaphosphate and 2; 4-diamino-6-diethoxy phosphoryl-1; 3, the combination of one or more in the 5-triazine.

5. halogen-free flame-retardant adhesive composition according to claim 4 is characterized in that it also comprises mineral filler, and described mineral filler consumption is 5-60 part.

6. halogen-free flame-retardant adhesive composition according to claim 5 is characterized in that it also comprises solidifying agent promotor, and described solidifying agent accelerator level is 0.1-1 part.

7. halogen-free flame-retardant adhesive composition according to claim 6 is characterized in that, described solidifying agent promotor is adopted one or more mixing in imidazolium compounds, three organic phosphine compounds, quaternary ammonium salt and the fluoroborate.

8. halogen-free flame-retardant adhesive composition according to claim 7 is characterized in that it also comprises phosphonium flame retardant, and described phosphonium flame retardant addition is 5-15 part.

9. halogen-free flame-retardant adhesive composition according to claim 8 is characterized in that, it also comprises 0.1-3 part oxidation inhibitor.

10. flexible copper-clad plate, it has electrical insulating film, bonding coat and Copper Foil, and described bonding coat is formed by the described halogen-free flame-retardant adhesive preparation of compositions of the arbitrary claim of claim 1～9.