JP5223660B2 - Resin composition, prepreg and laminate - Google Patents

Description

  The present invention relates to a resin composition, a prepreg, and a laminate.

  With recent demands for higher functionality and lighter, thinner and smaller electronic devices, electronic components have been increasingly integrated and densely packaged.

  Thermosetting resins typified by epoxy resins and the like are widely used for electrical and electronic equipment parts because of their excellent characteristics. These thermosetting resins are often given flame retardancy in order to ensure safety against fire. Conventionally, halogen-containing compounds such as brominated epoxy resins have been generally used as a method for making these thermosetting resins flame-retardant.

  However, halogen-containing compounds have a high degree of flame retardancy, but there is a concern that toxic gases such as dioxins are generated when burned.

  For these reasons, studies have been made on the use of phosphorus-based flame retardants as flame retardants, but there has been a concern that heat resistance will be reduced (see, for example, Patent Document 1).

Moreover, since an epoxy resin is generally a powdery solid, a prepreg which is added as a resin composition and impregnated with the resin is poor in flexibility, and is easily broken and cracked when stress is applied. . In particular, when the prepreg before heat forming is cut to a predetermined size, the resin is easily broken, so the resin scatters from the cut part, resulting in a so-called powder falling phenomenon, and the copper foil and the prepreg are stacked and heated. When molding, the resin may adhere to the surface of the copper foil. It is difficult to remove the resin adhering to the surface of the copper foil after heat and pressure molding, and the copper foil may remain during circuit processing, resulting in a circuit failure.
JP 2007-182544 A

  The present invention provides a resin composition, a prepreg, and a laminate that achieve excellent flame retardancy without using a halogen-containing compound, reduce dust generation, and have excellent heat resistance.

The present invention is achieved by the following (1) to (5).
(1) A resin composition used only for impregnating a base material to form a sheet-like prepreg,
100 parts by weight of epoxy resin, a curing agent and 105 parts by weight of aluminum hydroxide,
The epoxy resin is
An epoxy resin (a) having a naphthalene skeleton and not containing a phosphorus-containing functional group;
A phosphorus-containing epoxy resin (b) represented by the following formula (7);
An epoxy resin (c) comprising a bisphenol A-type structural unit and a hydrocarbon-based structural unit,

(In the formula, n is an average of 60 values.)
The epoxy resin (c) composed of the bisphenol A-type structural unit and the hydrocarbon-based structural unit is represented by the following general formula (6),

(In the formula, R ₁ and R ₂ each represent a methyl group. R _{3 to} R ₆ each represent a hydrogen atom or a methyl group. X represents an ethyleneoxyethylene group, a di (ethyleneoxy) ethylene group, a tri (ethyleneoxy group). ) Represents an ethylene group, a propyleneoxypropylene group, a di (propyleneoxy) propylene group, a tri (propyleneoxy) propylene group, or an alkylene group having 2 to 15 carbon atoms, and n is n> 0.
The content of the epoxy resin (a) having the naphthalene skeleton and not containing a phosphorus-containing functional group is 70% by weight or more and 85% by weight or less with respect to the epoxy resin,
The content of the phosphorus-containing epoxy resin (b) represented by the formula (7) is 7% by weight or more and 20% by weight or less with respect to the epoxy resin,
Content of the epoxy resin (c) which consists of the said bisphenol A type structural unit and a hydrocarbon type structural unit is 5 to 20 weight% with respect to the said epoxy resin, The resin composition characterized by the above-mentioned.

(2 ) The resin composition according to (1 ), wherein the epoxy resin (a) having the naphthalene skeleton and not containing a phosphorus-containing functional group is represented by the following general formula (5).

(R ₁ and R ₂ are alkylene groups represented by CH ₂ , C ₂ H _{4 and the} like.
n is 0 or more and 2 or less. R ₁ and R ₂ may be the same or different. )

(3 ) The phosphorus-containing epoxy resin (b) has a weight average molecular weight of 20,000 or more and 70,000 or less, and the phosphorus content is 3% or more and 6% or less (1) or (2) The resin composition described in 1 .
(4 ) A prepreg obtained by impregnating a base material with the resin composition according to any one of (1) to ( 3 ).
( 5 ) A laminate obtained by molding one or more prepregs according to ( 4 ) above.

  ADVANTAGE OF THE INVENTION According to this invention, while achieving the outstanding flame retardance without using a halogen-containing compound, dust generation can be reduced and the resin composition, prepreg, and laminated board which were excellent in heat resistance can be provided.

  Hereinafter, the resin composition, prepreg and laminate of the present invention will be described in detail.

  The resin composition of the present invention is formed by directly forming a resin composition on a metal foil as a base material and using it as a copper foil with a resin, or impregnating a glass fiber base material with a resin composition as a base material to form a prepreg. It can be used as an interlayer insulating material, or can be used as a laminate by laminating a prepreg and a metal foil and heating and pressing.

  The resin composition of the present invention is a resin composition used for impregnating a base material to form a sheet-like prepreg, which includes an epoxy resin and a curing agent, and the epoxy resin has a naphthalene skeleton. And an epoxy resin (a) containing no phosphorus-containing functional group, a phosphorus-containing epoxy resin (b), and an epoxy resin (c) comprising a bisphenol A-type structural unit and a hydrocarbon-based structural unit. To do.

  Moreover, the prepreg of the present invention is characterized in that a base material is impregnated with the above-mentioned resin composition.

  Moreover, the laminated board of the present invention is formed by molding one or more of the above-described prepregs.

  First, the resin composition of the present invention will be described.

  The resin composition of the present invention contains an epoxy resin, and the epoxy resin has a naphthalene skeleton and does not contain a phosphorus-containing functional group (a), a phosphorus-containing epoxy resin (b), and a bisphenol A type. And an epoxy resin (c) composed of a structural unit and a hydrocarbon-based structural unit. Thereby, while achieving a flame retardance without using a halogen-containing compound, dust generation can be reduced and the laminated board excellent in heat resistance can be obtained.

  Although it does not specifically limit as phosphorus containing epoxy resin (b), The compound represented by following General formula (1) is used suitably. The phosphorus-containing epoxy resin has a phosphorus-containing functional group in the skeleton.

(In the formula, X is selected from the general formulas (2) and (3). N is a value of 20 or more and 300 or less.)

(Wherein, Y is one selected from the general formula _{(4), R} 11 _{~R 13} represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl _{group, R} 11 to R Two or more of ₁₃ may be the same.)

(In the formula, Y is selected from the general formula (4), R _{21 to} R ₂₄ represent any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group, and R _{21 to} R Two or more of ₂₄ may be the same.)

_(Wherein, R 31 _{to R 38} is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, represents either a phenyl _group, more than two of R 31 _{to R 38} may be the same. )

Among these, the phosphorus-containing epoxy resin (b) represented by the following formula (7) is preferable.

(In the formula, n is an average of 60 values.)
Although it does not specifically limit as a weight average molecular weight of a phosphorus containing epoxy resin, It is preferable that it is 20,000 or more and 70,000 or less.

  Within this range, resin dusting can be suppressed and heat resistance is not reduced. Further, the phosphorus content of the phosphorus-containing epoxy resin (b) is preferably 3% or more and 6% or less, more preferably 4% or more and 5% or less.

  Although content of a phosphorus containing epoxy resin (b) is not specifically limited, It is preferable that it is 5 to 30 weight% with respect to an epoxy resin. If it is the range of this content, heat resistance can be maintained, without reducing a flame retardance. Even within this range, the content is preferably 10% by weight or more and 20% by weight or less.

  Although it does not specifically limit as an epoxy resin (a) which has a naphthalene skeleton and does not contain a phosphorus containing functional group, The compound represented by following General formula (5) is used suitably. The epoxy resin (a) having a naphthalene skeleton and not containing a phosphorus-containing functional group is preferably an epoxy resin having one glycidyl group, preferably a plurality of glycidyl groups, in the naphthalene skeleton.

(R ₁ and R ₂ are alkylene groups represented by CH ₂ , C ₂ H _{4 and the} like.
n is 0 or more and 2 or less. R ₁ and R _{2 may be the} same or different. )


Among these, an epoxy resin (a) having a naphthalene skeleton represented by the following formula (8) and not containing a phosphorus-containing functional group is preferable.

(Where n is an average of 1 values)

The content of the epoxy resin (a) having a naphthalene skeleton and not containing a phosphorus-containing functional group is not particularly limited, but is preferably 15% by weight or more and less than 70% by weight with respect to the epoxy resin. If the content is within the above range, dust generation can be suppressed without lowering the heat resistance.

  As the epoxy resin (c) composed of a bisphenol A structural unit and a hydrocarbon-based structural unit, a compound represented by the following general formula (6) is suitable.

(In the formula, R ₁ and R ₂ each represent a hydrogen atom or a methyl group. R _{3 to} R ₆ each represent a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom. X represents an ethyleneoxyethyl group, di ( Ethyleneoxy) represents an ethyl group, a tri (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propyleneoxy) propyl group, a tri (propyleneoxy) propyl group, or an alkylene group having 2 to 15 carbon atoms. , N is n> 0.)

The content of the epoxy resin composed of the bisphenol A-type structural unit and the hydrocarbon-based structural unit is not particularly limited, but is optimally 5% by weight or more and 30% by weight or less. Within this range, dust generation can be suppressed without reducing heat resistance and flame resistance. If the amount is less than 5% by weight, the dust generation property is lowered. If the amount is more than 30% by weight, heat resistance and flame resistance may be lowered.

  The resin composition of the present invention comprises an epoxy resin (a) having a naphthalene skeleton and not containing a phosphorus-containing functional group, a phosphorus-containing epoxy resin (b), a bisphenol A-type structural unit and a hydrocarbon-based structural unit. The epoxy resin (c) is contained, but other epoxy resins such as a bisphenol type epoxy resin, a novolac type epoxy resin, and a cresol novolak type epoxy resin can be used as long as they do not contradict the object of the present invention. Furthermore, as other resins, it is possible to add a phenoxy resin, a polyimide resin, a phenol resin, and the like, and a curing agent, a curing accelerator, a phosphorus flame retardant, a coupling agent, a filler, and other components.

  The prepreg of the present invention is obtained by impregnating a base material with the above resin composition. Thereby, the prepreg excellent in various characteristics, such as heat resistance, can be obtained.

  Examples of the base material used in the prepreg of the present invention include glass fiber base materials such as glass fiber cloth and glass non-woven cloth, inorganic fiber base materials such as fiber cloth and non-fiber cloth containing inorganic compounds other than glass, and aromatic polyamide resins. And organic fiber base materials composed of organic fibers such as polyamide resin, aromatic polyester resin, polyester resin, polyimide resin, and fluororesin. Among these base materials, glass fiber base materials represented by glass woven fabric are preferable in terms of strength and water absorption.

  Examples of the method of impregnating the substrate with the resin composition obtained in the present invention include, for example, a method in which a resin varnish is prepared by dissolving the resin composition in a solvent, and the substrate is immersed in the resin varnish. The method of apply | coating a varnish to a base material, the method of spraying a resin varnish on a base material with a spray apparatus, etc. are mentioned. Among these, the method of immersing the base material in the resin varnish is preferable. Thereby, the impregnation property of the resin composition with respect to a base material can be improved. In addition, when a base material is immersed in a resin varnish, a normal impregnation coating device can be used.

  The solvent used in the resin varnish desirably has good solubility in the resin composition, but a poor solvent may be used as long as it does not have an adverse effect. Examples of the solvent exhibiting good solubility include dimethylformamide.

  The solid content in the resin varnish is not particularly limited, but is preferably 40 to 80% by weight, particularly preferably 50 to 65% by weight, based on the solid content of the resin composition. Thereby, the impregnation property to the base material of a resin varnish can further be improved.

  A prepreg can be obtained by impregnating the substrate with the resin composition and drying at a predetermined temperature, for example, 80 to 200 ° C.

  Next, a laminated board is demonstrated.

  The laminate of the present invention is formed by molding at least one prepreg described above. Thereby, the laminated board which has the outstanding heat resistance and adhesiveness, and was excellent in the flame retardance can be obtained.

  In the case of a single prepreg, a metal foil or film is stacked on both upper and lower surfaces or one surface.

  Two or more prepregs can be laminated. When two or more prepregs are laminated, a metal foil or film is laminated on the outermost upper and lower surfaces or one surface of the laminated prepregs.

  Next, a laminate can be obtained by heating and pressurizing a laminate of a prepreg and a metal foil or the like.

  The heating temperature is not particularly limited, but is preferably 150 to 240 ° C, and particularly preferably 180 to 220 ° C.

  Moreover, the pressure to pressurize is not particularly limited, but is preferably 2 to 5 MPa, and particularly preferably 2.5 to 4 MPa.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to this.

Example 1
(1) Preparation of resin varnish: 110 parts by weight of dimethylformamide solvent, 0.2 parts by weight of 2-ethyl-4-methylimidazole, 5.2 parts by weight of dicyandiamide, ESN-375 (manufactured by Tohto Kasei Co., Ltd.) as a naphthalene type epoxy resin 80 parts by weight, 10 parts by weight of EXA-4816 (manufactured by DIC) represented by the general formula (6) as a resin composed of a bisphenol A type epoxy resin and a hydrocarbon resin, and a phosphorus-containing epoxy resin 10 parts by weight of ERF001M30 (manufactured by Tohto Kasei Co., Ltd.) represented by formula (7) and having an average n number of 60 are added, and after stirring for 60 minutes, 105 weights of aluminum hydroxide (CL-303, manufactured by Sumitomo Chemical Co., Ltd.) is used as a filler. And the mixture was stirred for 60 minutes to obtain a resin varnish.
(2) Manufacture of prepreg Using the resin varnish described above, 100 parts by weight of glass fiber cloth (thickness 0.18 mm, manufactured by Nitto Boseki Co., Ltd.) was impregnated with 80 parts by weight of resin varnish in a solid content, and 190 ° C. The prepreg having a resin content of 44.4% by weight was produced by drying in a drying oven for 5 minutes.
(3) Manufacture of laminated board Six sheets of the above prepregs are stacked, electrolytic copper foils with a thickness of 35 μm are stacked on top and bottom, and heat-press molding is performed at a pressure of 4 MPa and a temperature of 220 ° C. for 180 minutes, and both sides have a thickness of 1.2 mm. A copper clad laminate was obtained.

(Examples 2 to 5)
A resin varnish was prepared in the same manner as in Example 1 with the blending amounts shown in Table 1, and a prepreg and a laminate were obtained.

(Comparative Examples 1-5)
The resin varnish was prepared in the same manner as in Example 1 with the blending amounts shown in Table 1, and prepregs and laminates were obtained.

-Evaluation method The following evaluation was performed about the laminated board obtained by each Example and the comparative example. Each evaluation is shown below together with the evaluation method. The obtained results are shown in Table 1.
(1) Glass transition temperature The glass transition temperature was determined from the peak temperature of tan δ by a viscoelastic method.
(2) Solder heat resistance The solder heat resistance was measured in accordance with JIS C 6481. The measurement was performed after boiling for 2 hours and after immersion in a solder bath at 260 ° C. for 120 seconds, the presence or absence of abnormalities was examined. .
(3) Flame retardancy Flame retardancy was evaluated according to the UL vertical method.
(4) Dust generation property The prepreg obtained above is cut into a size of 100 mm × 100 mm, and 20 sheets are stacked. Next, the piled prepreg is dropped 10 times on a paper drawn down from a height of 50 mm. The total weight of the resin component and paper generated from the dropped prepreg was measured, and the dust generation property was evaluated as the amount of dust generated by subtracting the weight of the paper. The amount of dust generation was evaluated as “◯” when 0.05 g or less, and “x” when 0.05 g or more.

Claims (5)

A resin composition used only for impregnating a base material to form a sheet-like prepreg,
100 parts by weight of epoxy resin, a curing agent and 105 parts by weight of aluminum hydroxide,
The epoxy resin is
An epoxy resin (a) having a naphthalene skeleton and not containing a phosphorus-containing functional group;
A phosphorus-containing epoxy resin (b) represented by the following formula (7);
An epoxy resin (c) comprising a bisphenol A-type structural unit and a hydrocarbon-based structural unit,

(In the formula, n is an average of 60 values.)
The epoxy resin (c) composed of the bisphenol A-type structural unit and the hydrocarbon-based structural unit is represented by the following general formula (6),

(In the formula, R ₁ and R ₂ each represent a methyl group. R _{3 to} R ₆ each represent a hydrogen atom or a methyl group. X represents an ethyleneoxyethylene group, a di (ethyleneoxy) ethylene group, a tri (ethyleneoxy group). ) Represents an ethylene group, a propyleneoxypropylene group, a di (propyleneoxy) propylene group, a tri (propyleneoxy) propylene group, or an alkylene group having 2 to 15 carbon atoms, and n is n> 0.
The content of the epoxy resin (a) having the naphthalene skeleton and not containing a phosphorus-containing functional group is 70% by weight or more and 85% by weight or less with respect to the epoxy resin,
The content of the phosphorus-containing epoxy resin (b) represented by the formula (7) is 7% by weight or more and 20% by weight or less with respect to the epoxy resin,
Content of the epoxy resin (c) which consists of the said bisphenol A type structural unit and a hydrocarbon type structural unit is 5 to 20 weight% with respect to the said epoxy resin, The resin composition characterized by the above-mentioned. The resin composition according to claim 1, wherein the epoxy resin (a) having the naphthalene skeleton and not containing a phosphorus-containing functional group is represented by the following general formula (5).

(R ₁ and R ₂ are alkylene groups represented by CH ₂ , C ₂ H _{4 and the} like.
n is 0 or more and 2 or less. R ₁ and R ₂ may be the same or different. )   The resin composition according to claim 1 or 2, wherein the phosphorus-containing epoxy resin (b) has a weight average molecular weight of 20,000 or more and 70,000 or less, and a phosphorus content of 3% or more and 6% or less. .   A prepreg comprising a substrate impregnated with the resin composition according to any one of claims 1 to 3.   A laminate obtained by molding one or more prepregs according to claim 4.