WO2021132495A1 - 熱硬化性樹脂組成物、プリプレグ、積層板、プリント配線板及び半導体パッケージ - Google Patents
熱硬化性樹脂組成物、プリプレグ、積層板、プリント配線板及び半導体パッケージ Download PDFInfo
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- WO2021132495A1 WO2021132495A1 PCT/JP2020/048522 JP2020048522W WO2021132495A1 WO 2021132495 A1 WO2021132495 A1 WO 2021132495A1 JP 2020048522 W JP2020048522 W JP 2020048522W WO 2021132495 A1 WO2021132495 A1 WO 2021132495A1
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- 238000007348 radical reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- LTURHSAEWJPFAA-UHFFFAOYSA-N sulfuric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OS(O)(=O)=O.NC1=NC(N)=NC(N)=N1 LTURHSAEWJPFAA-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Definitions
- thermosetting resin compositions prepregs, laminated boards, printed wiring boards and semiconductor packages.
- the laminated board for the printed wiring board is required to have excellent low thermal expansion property and the like.
- a prepreg containing a resin composition and a glass cloth is generally cured and integrally molded.
- the prepreg can be reduced in thermal expansion by increasing the filling of an inorganic filler such as silica (see, for example, Patent Document 1).
- an inorganic filler such as silica
- the glass cloth and the inorganic filler are used when removing the smear (desmear) that occurs when a through hole is formed in the prepreg by CO 2 laser processing or the like. Etc. tend to be exposed and the reliability of the product tends to decrease. In particular, since CO 2 laser machining produces a large amount of smear compared to drilling, it is necessary to sufficiently remove the smear. Therefore, the prepreg, and thus the laminated board, is further improved in desmear resistance. Is required.
- an object of the present disclosure is to provide a thermosetting resin composition capable of achieving both low thermal expansion property and desmear resistance, and a prepreg, a laminated board, a printed wiring board, and a semiconductor package using the thermosetting resin composition. is there.
- One aspect of this embodiment relates to the following [1] to [14].
- thermosetting resin composition A maleimide compound having at least one N-substituted maleimide group and (b) an inorganic filler are contained, and the content of the (b) inorganic filler is a thermosetting resin composition.
- a thermosetting resin composition having a content of 53 to 65% by volume based on the total amount of the substance.
- thermosetting resin composition containing a compound having at least two unsaturated aliphatic hydrocarbon groups.
- the component (a) contains a reaction product of (a1) a maleimide compound having at least two N-substituted maleimide groups and (a2) a silicone compound having at least two primary amino groups.
- the maximum of the peak of the volume-based particle size distribution of the component (b) exists in both the range of 0.01 ⁇ m or more and less than 0.1 ⁇ m and the range of 0.1 ⁇ m or more and 10 ⁇ m or less.
- thermosetting resin composition according to any one.
- the component (c) has at least two unsaturated aliphatic hydrocarbon groups (c2) and is either the following general formula (c2-1) or the following general formula (c2-2).
- the unsaturated aliphatic hydrocarbon group contained in the component (c) is selected from the group consisting of a vinyl group, an isopropenyl group, a 1-propenyl group, an allyl group, a 1-methylallyl group and a 3-butenyl group.
- the prepreg according to the above [9] which has a thickness of 40 to 300 ⁇ m.
- [11] A laminated board containing the prepreg according to the above [9] or [10].
- [12] A metal-clad laminate in which metal foils are arranged on one side or both sides of the laminate according to the above [11].
- [13] A printed wiring board obtained by forming a circuit on the laminated board according to the above [11] or the metal-clad laminated board according to the above [12].
- [14] A semiconductor package containing the printed wiring board and semiconductor element according to the above [13].
- thermosetting resin composition capable of achieving both low thermal expansion property and desmear resistance, a prepreg, a laminated board, a printed wiring board, and a semiconductor package using the thermosetting resin composition.
- Example 4 It is an image figure for demonstrating the particle size distribution of (b) an inorganic filler used in this disclosure.
- Example 4 it is a scanning electron microscope (SEM) photograph (magnification: 5,000 times) of the substrate surface after desmear treatment.
- the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. Further, the lower limit value and the upper limit value of the numerical range are arbitrarily combined with the lower limit value or the upper limit value of the other numerical range, respectively.
- the description of "10 or more” means numerical values exceeding 10 and 10, and the same applies when the numerical values are different. Further, for example, the description "10 or less” means numerical values of 10 and less than 10, and the same applies when the numerical values are different. Further, as for each component and material exemplified in this specification, one kind may be used alone or two or more kinds may be used in combination unless otherwise specified.
- each component in the composition is the total amount of the plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition.
- resin component means (a) component and (c) component, (d) component used as necessary, (f) monoamine compound, and other optional resin. This does not include (b) inorganic fillers, (e) curing accelerators, additives and the like.
- solid content refers to components in the resin composition other than volatile substances such as water and solvents described below. That is, the solid content includes liquid, starch syrup-like or wax-like substances at room temperature around 25 ° C., and does not necessarily mean that it is solid. An embodiment in which the items described in the present specification are arbitrarily combined is also included in the present embodiment.
- thermosetting resin composition is (a) a maleimide compound having at least one N-substituted maleimide group [hereinafter, may be referred to as a component (a). ] And (b) Inorganic filler [Hereinafter, it may be referred to as the component (b). ], And the content of the inorganic filler (b) is 53 to 65% by volume based on the total amount of the thermosetting resin composition. c) A compound having at least two unsaturated aliphatic hydrocarbon groups [hereinafter, may be referred to as a component (c). ] Is a thermosetting resin composition containing.
- thermosetting property is improved while improving the low thermal expansion property by increasing the content of the component (b) to the above range.
- component (c) in the resin composition, the desmear resistance could be improved.
- the thermosetting resin composition of the present embodiment can be made excellent in heat resistance and low thermal expansion.
- the market demand for low thermal expansion is becoming stricter year by year, and the low thermal expansion is insufficient only by using the component (a).
- the content of the component (b) is further increased. By increasing it, excellent low thermal expansion can be exhibited.
- the component (a) may be referred to as a maleimide compound having at least two N-substituted maleimide groups (hereinafter, referred to as the component (a1)) from the viewpoint of heat resistance and low thermal expansion.
- a silicone compound having the component (a1) and (a2) at least two primary amino groups [hereinafter, (A2) It may be referred to as a component. ] And [Hereafter, it may be referred to as a modified maleimide resin (A). ] Is more preferable. It is also preferable that the component (a) contains the component (a1) and the modified maleimide resin (A).
- a maleimide compound having at least two N-substituted maleimide groups As the component (a1), a maleimide compound represented by the following general formula (a1-1) is more preferable.
- X a1 is a group represented by the following general formulas (a1-2), (a1-3), (a1-4), (a1-5) or (a1-6)).
- R a1 are each independently, .P1 an aliphatic hydrocarbon group, or a halogen atom having 1-5 carbon atoms is an integer of 0-4. * Represents a binding site.
- R a2 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, respectively.
- X a2 is an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms.
- Q1 is an integer of 0 to 4 independently. Yes. * Represents the binding site.
- R a3 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, respectively.
- X a3 is an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms.
- r1 is an independently integer of 0 to 4. * Represents the bond site.
- n1 is an integer from 1 to 10. * Represents the binding site.
- n2 is a number from 0 to 5. * Represents the binding site.
- R a4 each independently, .U1 an aliphatic hydrocarbon group having a hydrogen atom or a C 1-5 an integer of 1-8. * Represents a binding site.
- R a1 represents a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, Examples thereof include a t-butyl group and an n-pentyl group.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
- Ra1 an aliphatic hydrocarbon group is preferable.
- p1 is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 from the viewpoint of availability. When p1 is an integer of 2 or more, the plurality of Ra1s may be the same or different.
- aliphatic hydrocarbon group having 1 to 5 carbon atoms R a2 represents, as the halogen atom include the same ones as those R a1 represents.
- the aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and further preferably an ethyl group.
- Ra2 an aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferable.
- the alkylene group having a carbon number of 1 to 5 X a2 represents, methylene group, 1,2-dimethylene group, a 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group and the like Be done.
- the alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a methylene group.
- an isopropylidene group is preferable.
- X a2 among the above options, an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, and a group represented by the general formula (a1-3') are preferable, and the general formula (a1-3') is preferable.
- the group represented by') is more preferable.
- q1 is an integer of 0 to 4 independently, and is preferably an integer of 0 to 2, more preferably 0 or 2, from the viewpoint of availability.
- the plurality of Ra2s may be the same or different from each other.
- aliphatic hydrocarbon group having 1 to 5 carbon atoms R a3 represents, as the halogen atom include the same ones as those R a2 represents.
- Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X a3 are the same as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X a2. Be done.
- X a3 is preferably an alkylidene group having 2 to 5 carbon atoms, and more preferably an isopropylidene group.
- r1 is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 from the viewpoint of availability.
- the plurality of Ra3s may be the same or different from each other.
- a maleimide compound in which X a1 in the general formula (a1-1) is represented by the general formula (a1-3) is used as the component (a1) used as the raw material of the modified maleimide resin (A).
- a maleimide compound in which X a2 in which X a2 is represented by the general formula (a1-3') in the general formula (a1-3) is more preferable.
- n1 is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3 from the viewpoint of availability.
- the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a4 and the halogen atom are the same as those represented by R a1 in the general formula (a1-2).
- the recited aliphatic hydrocarbon group and a halogen atom preferably 1 to 5 carbon atoms of R a4 is the same as for R a1.
- u1 is an integer of 1 to 8, preferably an integer of 1 to 3, and more preferably 1.
- the component (a1) used without reacting with the component (a2) is described in the general formula (a1-1) from the viewpoint of increasing the solubility of the modified maleimide resin (A) in an organic solvent.
- a maleimide compound that is, polyphenylmethane maleimide in which X a1 is represented by the general formula (a1-4) is preferable.
- component (a1) bis (4-maleimidephenyl) methane, bis (4-maleimidephenyl) sulfone, 3,3'-dimethyl, from the viewpoint of high reaction rate and higher heat resistance.
- -5,5'-diethyl-4,4'-diphenylmethanebismaleimide 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane is preferred, and 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane is preferred.
- Phenyl] Propane is more preferred.
- a silicone compound having an amino group at at least one molecular terminal is preferable, and a silicone compound having an amino group at both molecular ends is preferable. Is more preferable. Further, it may be a silicone compound having an amino group in the side chain, or may be a silicone compound having an amino group in the side chain and at least one of the molecular terminals. Among these, a silicone compound having amino groups at both ends of the molecule is particularly preferable as the component (a2), and as such a silicone compound, an amino-modified silicone compound represented by the following general formula (a2-1) is preferable. Can be mentioned.
- the plurality of Ra 21s independently represent an alkyl group, a phenyl group, or a substituted phenyl group, and may be the same or different from each other.
- R a22 and R a23 each independently represent a single bond or an organic group.
- n3 represents an integer of 2 to 50.
- an alkyl group having 1 to 5 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and an alkyl group having 1 or 2 carbon atoms is more preferable.
- Groups are even more preferred.
- Specific examples of Ra21 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like, and among these, a methyl group is preferable.
- Examples of the substituent in the substituted phenyl group represented by Ra 21 include an alkyl group, an alkenyl group, an alkynyl group and the like, and among these, an alkyl group is preferable.
- the alkyl group the same group as described above is preferably mentioned.
- a phenyl group or a methyl group is preferable, and a methyl group is more preferable, from the viewpoint of solubility with other resins.
- Examples of the organic group represented by R a22 or Ra23 include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, an ether group, or a linking group in which these are combined.
- a substituted or unsubstituted alkylene group a substituted or unsubstituted arylene group is preferable, and a substituted or unsubstituted alkylene group is more preferable.
- the alkylene group include a methylene group, an ethylene group, a trimethylene group and the like, and a trimethylene group is preferable.
- the substituent of the alkylene group is not particularly limited, and examples thereof include an aryl group having 6 to 10 carbon atoms.
- the arylene group include a phenylene group and a naphthylene group.
- the substituent of the arylene group is not particularly limited, and examples thereof include an alkyl group having 1 to 5 carbon atoms.
- R a22 and R a23 may be a single bond or an organic group, but are preferably an organic group.
- the functional group equivalent of the component (a2) is not particularly limited, but is preferably 400 to 6,000 g / eq, more preferably 400 to 5,000 g / eq, and further preferably 400 to 5,000 g / eq from the viewpoint of low thermal expansion. It is 400 to 3,500 g / eq, particularly preferably 500 to 1,500 g / eq, and most preferably 700 to 1,000 g / eq.
- the component (a2) one type may be used alone, or two or more types may be used in combination.
- ком ⁇ онент (a2) a commercially available product can be used.
- Commercially available products include [I] "KF-8010” (functional group equivalent: 430 g / eq), "X-22-161A” (functional group equivalent: 800 g / eq), which have amino groups at both ends.
- X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3, BY-16-853B, and XF42-C5379 are available.
- X-22-161A, X-22-161B, KF-8012, and XF42-C5379 are preferable.
- Azomethine-modified siloxane obtained by reacting with a compound [hereinafter, may be referred to as an azomethine-modified siloxane (a2') or (a2') component. ] Is more preferable.
- the dialdehyde compound include an aliphatic dialdehyde compound and an aromatic dialdehyde compound. Among these, aromatic dialdehyde compounds are preferable.
- the aromatic dialdehyde compound has an aromatic hydrocarbon group, and may also have an aliphatic hydrocarbon group as long as it has an aromatic hydrocarbon group.
- a compound having a structure of an aromatic hydrocarbon group-an aliphatic hydrocarbon group-an aromatic hydrocarbon group in the molecule is also included in the aromatic aldehyde compound.
- aromatic dialdehyde compound examples include terephthalaldehyde, isophthalaldehyde, o-phthalaldehyde, 2,2'-bipyridine-4,4'-dicarboxyaldehyde and the like.
- terephthalaldehyde may be selected from the viewpoints that lower thermal expansion is possible, the reactivity at the time of reaction is high, the solubility in an organic solvent is excellent, and the terephthalaldehyde is commercially available. ..
- the method for producing the azomethine-modified siloxane (a2') is not particularly limited.
- the amino-modified silicone compound represented by the general formula (a2-1) and the dialdehyde compound are dehydrated in an organic solvent. It can be produced by subjecting it to a condensation reaction.
- the amount of the amino-modified silicone compound represented by the general formula (a2-1) and the dialdehyde compound used is, for example, the first of the amino-modified silicone compounds represented by the general formula (a2-1).
- the number of secondary amino groups [amount of amino-modified silicone compound used / primary amino group equivalent of amino-modified silicone compound] is 1 of the number of aldehyde groups of dialdehyde compound [amount of dialdehyde compound used / aldehyde group equivalent of dialdehyde compound]. .
- the method for producing the modified maleimide resin (A) is not particularly limited, but the modified maleimide is formed by adding the amino group of the component (a2) to the carbon-carbon double bond of the maleimide group of the component (a1).
- the resin (A) can be produced.
- the modified maleimide resin (A) may be produced by reacting the (f) monoamine compound described later together, and the (f) monoamine compound is not used in the production of the modified maleimide resin (A). May be good.
- the modified maleimide resin (A) is preferably produced while being heated and kept warm in an organic solvent.
- the reaction temperature is preferably 70 to 200 ° C., more preferably 70 to 150 ° C., and even more preferably 100 to 130 ° C.
- the reaction time is preferably 0.1 to 10 hours, more preferably 1 to 6 hours.
- reaction catalyst can be used for the production of the modified maleimide resin (A), if necessary.
- the reaction catalyst is not particularly limited, and examples thereof include amines such as triethylamine, pyridine and tributylamine; imidazoles such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine. These may be used alone or in combination of two or more.
- the number of maleimide groups of the component (a1) [the amount of the component (a1) used (g) / the functional group equivalent of the maleimide group of the component (a1) (g / eq)] is (a2).
- the number of amino groups of the component [the amount of the (a2) component used (g) / the functional group equivalent of the amino group of the (a2) component (g / eq)] is preferably 0.1 to 10 times, preferably 1 to 9 times. More preferably, 1.1 to 9 times is further preferable, and 2 to 8 times is particularly preferable. When it is 0.1 times or more, particularly 2 times or more, gelation is suppressed and the heat resistance tends to be good, and when it is 10 times or less, the solubility in an organic solvent and heat resistance are good. It tends to be.
- the modified maleimide resin (A) is preferably produced in the presence of an organic solvent.
- the organic solvent is not particularly limited, but is an alcohol solvent such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and an ether solvent such as tetrahydrofuran.
- Solvents aromatic solvents such as toluene, xylene and mesitylen; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethylsulfooxide and the like.
- organic solvent one type may be used alone, or two or more types may be used in combination.
- cyclohexanone, propylene glycol monomethyl ether, and methyl cellosolve are preferable from the viewpoint of solubility
- cyclohexanone and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity, and they are highly volatile and remain as a residual solvent during the production of prepreg.
- Propylene glycol monomethyl ether is more preferable because it is difficult.
- the content of the component (a) in the thermosetting resin composition of the present embodiment is not particularly limited, but is 30 to 99% by mass with respect to 100 parts by mass of the resin component in the thermosetting resin composition. Parts are preferable, 35 to 90 parts by mass is more preferable, 40 to 85 parts by mass is further preferable, and 45 to 80 parts by mass is particularly preferable.
- the component (a) contains the component (a1) and the modified maleimide resin (A)
- the contents of the component (a1) and the modified maleimide resin (A) are not particularly limited.
- the resin component in the thermosetting resin composition 10 to 60 parts by mass is preferable, 15 to 55 parts by mass is more preferable, 20 to 50 parts by mass is further preferable, and 20 parts by mass is preferable. Up to 40 parts by mass is particularly preferable.
- thermosetting resin composition of the present embodiment can obtain low thermal expansion property by containing (b) an inorganic filler in an amount of 53 to 65% by volume based on the total amount of the thermosetting resin composition.
- the content of (b) the inorganic filler is preferably 54 to 62% by volume, more preferably 55 to 60% by volume, still more preferably 56 to 59% by volume. It was found that when the content of the component (b) was 53% by volume or more based on the total amount of the thermosetting resin composition, the low thermal expansion property was excellent, but the desmear resistance was lowered. The desmear resistance was solved by containing the component (c) described later.
- the prepreg and the laminated board become highly elastic, and the effect of reducing the warp can be expected.
- the maximum of the peak of the particle size distribution of the component (b) is at least in the range of 0.01 ⁇ m or more and less than 0.1 ⁇ m.
- the maximum of the peak of the volume-based particle size distribution of the component (b) exists in both the range of 0.01 ⁇ m or more and less than 0.1 ⁇ m and the range of 0.1 ⁇ m or more and 10 ⁇ m or less.
- the content of the component (b) can be 53% by volume or more with respect to the total amount of the thermosetting resin composition.
- the particle size distribution is a volume-based frequency distribution.
- the maximum of the peak of the particle size distribution is the position where the frequency is the maximum value at the peak of the peak in the particle size distribution (volume basis) expressed as the frequency, and FIG. 1 is used. To explain, it means the maximum (B1) and the maximum (B2).
- the measurement is performed by a particle size distribution measuring device using a laser diffraction / scattering method.
- thermosetting resin composition in which the maximum particle size distribution peak is in the range of 0.01 ⁇ m or more and less than 0.1 ⁇ m (10 nm or more and less than 100 nm) and 0.1 ⁇ m or more and 10 ⁇ m or less. By containing it, there is a tendency that even more excellent low thermal expansion property and a higher elastic modulus can be obtained while maintaining good moldability.
- the component (b) is not particularly limited, but silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, Aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, silicon carbide, quartz powder, short glass fibers, fine glass powder, hollow glass, etc. Is mentioned, and it is preferable that it is at least one selected from the group consisting of these. As the glass, E glass, T glass, D glass and the like are preferably mentioned.
- silica is preferable from the viewpoint of dielectric properties, heat resistance and low thermal expansion.
- examples of silica include precipitated silica having a high water content produced by a wet method and dry silica produced by a dry method and containing almost no bound water or the like.
- the dry silica is further classified into crushed silica, fumed silica, molten spherical silica and the like depending on the manufacturing method.
- molten spherical silica is preferable from the viewpoint of low thermal expansion and fluidity when filled in a resin.
- the component (b) may be surface-treated with a coupling agent.
- the method of surface treatment with a coupling agent may be a method of surface-treating the inorganic filler before compounding by a dry method or a wet method, and by blending the surface-untreated inorganic filler with other components.
- a so-called inorganic blend treatment method may be used in which a silane coupling agent is added to the composition after the composition is prepared.
- the coupling agent include a silane-based coupling agent, a titanate-based coupling agent, a silicone oligomer and the like. Among these, silane-based coupling agents are preferable.
- silane coupling agent examples include epoxysilane-based coupling agents, aminosilane-based coupling agents, vinylsilane-based coupling agents, phenylsilane-based coupling agents, alkylsilane-based coupling agents, alkenylsilane-based coupling agents, and alkynylsilanes. Coupling agents, haloalkylsilane-based coupling agents, siloxane-based coupling agents, hydrosilane-based coupling agents, silazane-based coupling agents, alkoxysilane-based coupling agents, chlorosilane-based coupling agents, (meth) acrylic silane-based cups.
- Examples thereof include ringing agents, isocyanuratesilane-based coupling agents, ureidosilane-based coupling agents, mercaptosilane-based coupling agents, sulfidesilane-based coupling agents, and isocyanatesilane-based coupling agents.
- ringing agents isocyanuratesilane-based coupling agents, ureidosilane-based coupling agents, mercaptosilane-based coupling agents, sulfidesilane-based coupling agents, and isocyanatesilane-based coupling agents.
- aminosilane-based coupling agents are more preferable.
- the maximum peak of the particle size distribution may be referred to as a range of 0.01 ⁇ m or more and less than 0.1 ⁇ m [hereinafter, referred to as a particle size distribution range (b1). ] And a range of 0.1 ⁇ m or more and 10 ⁇ m or less [hereinafter, may be referred to as a particle size distribution range (b2). ], It is preferable to contain the inorganic filler present in both.
- This embodiment may be referred to as, for example, the maximum [maximum (B1)) of the peak of the particle size distribution in the particle size distribution range (b1). ]
- Inorganic filler hereinafter, may be referred to as (b1) inorganic filler.
- Inorganic filler (hereinafter, may be referred to as (b2) inorganic filler. ]
- the thermosetting resin composition As the inorganic filler (b1) and the inorganic filler (b2), one type may be used alone, or two or more types may be used in combination as long as the effects of the present embodiment are not impaired. Good.
- the particle size distribution range (b1) is preferably 0.02 ⁇ m or more and 0.08 ⁇ m or less (20 nm or more and 80 nm or less), and more preferably 0.02 ⁇ m or more and 0.05 ⁇ m or less from the viewpoint of low thermal expansion, elastic modulus and moldability. (20 nm or more and 50 nm or less), more preferably 0.02 ⁇ m or more and 0.04 ⁇ m or less (20 nm or more and 40 nm or less).
- the particle size distribution range (b2) is preferably 0.3 ⁇ m or more and 8 ⁇ m or less, more preferably 0.5 ⁇ m or more and 5 ⁇ m or less, and further preferably 0.5 ⁇ m or more and 3 ⁇ m or less from the viewpoint of low thermal expansion, elastic modulus and moldability. Particularly preferably, it is 0.5 ⁇ m or more and 1.5 ⁇ m or less.
- the particle size where the maximum peak (B1) existing in the particle size distribution range (b1) is located and the particle size where the maximum peak (B2) existing in the particle size distribution range (b2) is located is not particularly limited, but from the viewpoint of low thermal expansion, elasticity and moldability, a difference of 0.2 ⁇ m or more is preferable, a difference of 0.5 ⁇ m or more is more preferable, and 0 It is more preferable that there is a difference of 8.8 ⁇ m or more. Further, in the particle size distribution, the upper limit of the difference between the particle size at which the maximum (B1) is located and the particle size at which the maximum (B2) is located is not particularly limited, but the difference is preferably 5 ⁇ m or less.
- the "difference" in particle size is an absolute value. However, the difference in particle size is when there are two or more peaks in the particle size distribution range (b1), or when there are two or more peaks in the particle size distribution range (b2). , Refers to the difference between the largest peaks in each range.
- the average particle size of the (b1) inorganic filler is preferably 0.01 to 1 ⁇ m, more preferably 0.02 to 0.7 ⁇ m, still more preferably 0.04 to 0.5 ⁇ m, and particularly preferably 0.04 to 0.04 to. It is 0.2 ⁇ m.
- the average particle size of the (b2) inorganic filler is preferably 0.1 to 10 ⁇ m, more preferably 0.3 to 8 ⁇ m, still more preferably 0.5 to 5 ⁇ m, and particularly preferably 0.5 to 3 ⁇ m. Most preferably, it is 0.5 to 1.5 ⁇ m.
- the average particle size of the (b2) inorganic filler By setting the average particle size of the (b2) inorganic filler to 0.1 ⁇ m or more, it tends to be easy to maintain good fluidity when the (b2) inorganic filler is highly filled in the thermosetting resin composition.
- the average particle size of the inorganic filler (b2) By setting the average particle size of the inorganic filler (b2) to 10 ⁇ m or less, the probability of mixing coarse particles tends to be reduced, and the occurrence of defects due to the coarse particles tends to be suppressed. Further, by using the inorganic filler having the average particle size (b1) in combination, the fluidity of the thermosetting resin composition tends to be improved and the inorganic filler can be highly filled.
- the average particle size in the present specification is the particle size (volume average particle size) of a point corresponding to a volume of 50% when the cumulative frequency distribution curve by the particle size is obtained with the total volume of particles as 100%. This is to be measured with a particle size distribution measuring device using a laser diffraction / scattering method.
- the content of the (b1) inorganic filler in the (b) inorganic filler [(b1) inorganic filler / (b) inorganic filler] is from the viewpoint of (b) increasing the filling of the inorganic filler. , Preferably 0.1 to 20% by volume, more preferably 0.3 to 15% by volume, still more preferably 0.5 to 12% by volume, particularly preferably 1.0 to 10% by volume, most preferably 2.5. ⁇ 7.0% by volume.
- the inorganic filler is the above-mentioned preferable material, that is, silica (molten spherical silica), the same content as described above is preferable.
- ((C) A compound having at least two unsaturated aliphatic hydrocarbon groups
- the content of the component (b) is set to 53% by volume or more with respect to the total amount of the thermosetting resin composition, the low thermal expansion property is excellent, but the desmear resistance is lowered as it is.
- the desmear resistance was also improved by containing the component (c).
- the component (c) does not generate a secondary amino group during the reaction with the carbon-carbon double bond of the maleimide group, and the unreacted maleimide group reacts with the Diels-Alder reaction.
- the desmear resistance was not lowered by the absence of the secondary amino group, and the desmear resistance was improved by forming a structure resistant to oxidation by the Diels-Alder reaction. Guess.
- the component (c) one type may be used alone, or two or more types may be used in combination.
- the component (c) is preferably a compound having at least three unsaturated aliphatic hydrocarbon groups from the viewpoint of desmear resistance.
- the unsaturated aliphatic hydrocarbon group contained in the component (c) is not particularly limited, but is preferably an unsaturated aliphatic hydrocarbon group capable of radical reaction, and is preferably a vinyl group or an isopropenyl group. , 1-Propenyl group, allyl group, 1-methylallyl group, 3-butenyl group and the like, more preferably at least one selected from the group.
- an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms is preferable, an unsaturated aliphatic hydrocarbon group having 2 to 5 carbon atoms is more preferable, and a 1-propenyl group and an allyl group are preferable. Groups are even more preferred.
- the unsaturated aliphatic hydrocarbon is viewed as a whole.
- a group that cannot be said to be a hydrogen group is not included in the "unsaturated aliphatic hydrocarbon group" in the component (c).
- a compound (c1) having at least two unsaturated aliphatic hydrocarbon groups and having an aromatic hydrocarbon group may be referred to as a component (c1).
- (C2) A compound having at least two unsaturated aliphatic hydrocarbon groups and having a structure of either the following general formula (c2-1) or the following general formula (c2-2) [hereinafter, (C2) It may be referred to as a component. ] Etc. can be mentioned.
- the component (c1) one type may be used alone, or two or more types may be used in combination.
- the component (c2) one type may be used alone, or two or more types may be used in combination.
- the component (c) preferably contains at least one selected from the group consisting of the component (c1) and the component (c2), and an embodiment containing the component (c1) is also preferable. Aspects including the above are also preferable.
- * indicates a linking site to another group. The * is not particularly limited, but a mode in which it is directly linked to an unsaturated aliphatic hydrocarbon group is preferable. It is one of them.
- the aromatic hydrocarbon group of the component (c1) examples include benzene residues, naphthalene residues, biphenyl residues and the like. Among these, benzene residues and biphenyl residues are preferable.
- the “residue” refers to a monovalent or divalent or higher valent group obtained by extracting a hydrogen atom from a target compound.
- the aromatic hydrocarbon group may have a substituent, and examples of the substituent include, but are not limited to, a hydroxyl group and an alkoxyl group.
- Specific examples of the component (c1) include the following compounds. (In the formula, R c1 to R c3 are independently organic groups. M c1 is independently 0 or 1.
- n c1 and n c2 are both parts enclosed in brackets. Represents the number of repeating units of, and each is independently 1 to 100.)
- R c4 to R c7 are independently organic groups.
- M c2 and m c3 are independently 0 or 1.
- n c3 to n c6 are both enclosed in brackets. It represents the number of repeating units of the part that has been removed, and is 1 to 100 independently for each.
- R c8 and R c9 are independently organic groups.
- N c7 to n c10 each represent the number of repeating units of the part enclosed in parentheses, and each independently represents 1 to 100. Is.
- the organic groups represented by R c1 to R c9 include ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and tridecyl group.
- Alkyl group having 2 to 20 carbon atoms such as group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group; aryl group having 6 to 18 ring-forming carbon atoms such as phenyl group, biphenyl group and naphthyl group; benzyl group Examples thereof include an aralkyl group having 6 to 18 carbon atoms; an alicyclic hydrocarbon group having 5 to 18 carbon atoms such as an adamantyl group, a cyclohexyl group and a cyclopentadienyl group.
- the organic groups represented by R c1 , R c4 and R c6 may be bonded via -O- or -S-, that is, they are -O-organic group and -S-organic group. You may.
- the organic groups represented by R c1 to R c9 are preferably bulky organic groups among the above options, and are alkyl groups having 4 to 20 carbon atoms, aryl groups having 6 to 18 ring-forming carbon atoms, and ring-forming groups.
- An aralkyl group having 6 to 18 carbon atoms and an alicyclic hydrocarbon group having 5 to 18 carbon atoms are more preferable, an alkyl group having 4 to 20 carbon atoms, an aralkyl group having 6 to 18 carbon atoms forming a ring, and an aralkyl group having 5 to 18 carbon atoms.
- the alicyclic hydrocarbon group of is more preferred. Note that one when a plurality of R c1 in the molecule are present, plural of R c1 may each identical, may be different, and those that differ from the same thing coexist May be good. The same can be said for R c2 to R c9.
- m c1 to m c3 may be either 0 or 1 independently of each other. As n c1 to n c10 , 1 to 100 is preferable, and 3 to 30 is more preferable, respectively.
- component (c2) include the following compounds.
- R c2 is an aliphatic hydrocarbon group having 2 to 18 carbon atoms which may contain at least one selected from the group consisting of an ether group and a hydroxyl group.
- the R c2 is preferably a group represented by any of the following general formulas (i) to (iii). (Wherein, p c1 represents the number of repeating units of the methylene groups is an integer of 2 ⁇ 18 .p c2 represents the number of repeating units of oxyethylene groups, is 0 or 1. * Is the binding site. )
- the pc1 is preferably an integer of 2 to 10, more preferably an integer of 3 to 8, and even more preferably an integer of 3 to 5.
- the pc2 may be 0 or 1, but is preferably 1.
- the content of the component (c) in the thermosetting resin composition of the present embodiment is not particularly limited, but from the viewpoint of low thermal expansion and desmear resistance, the number of maleimide groups of the component (a).
- the ratio of the number of carbon-carbon double bonds in the component (c) to (c) [the number of carbon-carbon double bonds / the number of maleimide groups] can be adjusted with the goal of being 0.4 to 0.9.
- the content of the component (c) is preferably 2 to 80 parts by mass, more preferably 5 to 65 parts by mass, and further 8 to 45 parts by mass with respect to 100 parts by mass of the resin component of the thermosetting resin composition. preferable.
- the content of the component (c1) is 100 parts by mass of the resin component of the thermosetting resin composition from the viewpoint of low thermal expansion property and desmear resistance.
- 10 to 80 parts by mass is preferable, 15 to 65 parts by mass is more preferable, 25 to 45 parts by mass is further preferable, and 25 to 40 parts by mass is particularly preferable.
- the content of the component (c2) is 100 parts by mass of the resin component of the thermosetting resin composition from the viewpoint of low thermal expansion property and desmear resistance.
- 2 to 65 parts by mass is preferable, 2 to 40 parts by mass is more preferable, 2 to 25 parts by mass is further preferable, 5 to 20 parts by mass is particularly preferable, and 8 to 18 parts by mass is most preferable.
- thermosetting resin composition of the present embodiment is further referred to as (d) thermosetting resin [hereinafter, referred to as (d) component. ] May be contained.
- thermosetting resin composition of the present embodiment contains the component (d)
- the thermosetting resin composition of the present embodiment does not have to contain (d) the thermosetting resin. It is assumed that the component (d) does not include the component (a).
- an epoxy resin As the component (d), an epoxy resin, a phenol resin, an unsaturated imide resin (however, the component (a) is excluded), a cyanate resin, an isocyanate resin, a benzoxazine resin, an oxetane resin, an amino resin, and an unsaturated polyester resin.
- epoxy resin is preferable from the viewpoint of moldability and electrical insulation, and from the viewpoint of improving the adhesiveness with the metal foil.
- the (d) thermosetting resin the ICI viscosity at 150 ° C.
- the ICI viscosity measures a high shear rate known as an ICI viscometer, and is a viscosity measured by a cone plate type viscometer.
- epoxy resin bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, naphthalene.
- Skeleton-containing novolac type epoxy resin stillben type epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, triphenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy
- examples thereof include resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, polyfunctional phenols, polycyclic aromatic diglycidyl ether compound such as anthracene, and phosphorus-containing epoxy resin in which a phosphorus compound is introduced therein.
- naphthalene skeleton-containing novolac type epoxy resin and bisphenol F type are preferable, and a naphthalene skeleton-containing novolac type epoxy resin and bisphenol F type are preferable.
- Epoxy resins, bisphenol S-type epoxy resins, naphthalene-type epoxy resins, and dicyclopentadiene-type epoxy resins are more preferable, naphthalene-type epoxy resins and dicyclopentadiene-type epoxy resins are even more preferable, and naphthalene-type epoxy resins are particularly preferable.
- epoxy resin can be used.
- Commercially available products include naphthalene skeleton-containing novolac type epoxy resin [manufactured by Nippon Kayaku Co., Ltd., trade name: NC-7000L, ICI viscosity at 150 ° C.: 0.50 to 1.00 Pa ⁇ s], naphthalene type epoxy resin [ DIC Co., Ltd., trade name: HP-4032SS, ICI viscosity at 150 ° C.: 0.1 Pa ⁇ s or less] [DIC Co., Ltd., trade name: EXA-7311-G4, ICI viscosity at 150 ° C.: 0.
- thermosetting resin composition of the present embodiment contains (d) a thermosetting resin
- the content thereof is the thermosetting resin composition from the viewpoints of heat resistance, low thermal expansion property, and adhesion to a metal foil.
- 100 parts by mass of the resin component of the product 5 to 50 parts by mass is preferable, 10 to 40 parts by mass is more preferable, and 15 to 40 parts by mass is further preferable.
- thermosetting resin composition of the present embodiment may be referred to as (e) a curing accelerator [hereinafter, referred to as (e) component. ] May be contained.
- a curing accelerator hereinafter, referred to as (e) component.
- Ingredients include imidazoles and derivatives thereof; organophosphorus compounds such as phosphines and phosphonium salts, adducts of tertiary phosphines and quinones; secondary amines, tertiary amines, and quaternary amines. Examples include quaternary ammonium salts.
- the component (e) one type may be used alone, or two or more types may be used in combination.
- imidazoles and derivatives thereof are preferable from the viewpoints of heat resistance, flame retardancy, adhesion to metal foil, etc., and among them, curability at a relatively low temperature of 200 ° C. or lower is curable and moldable.
- a imidazole derivative obtained by reacting the group with an epoxy resin is more preferable.
- R e1 to R e4 are independently hydrogen atoms, aliphatic hydrocarbon groups having 1 to 5 carbon atoms, or phenyl groups.
- D is an alkylene group having 1 to 10 carbon atoms. Or an aromatic hydrocarbon group having 6 to 12 carbon atoms.
- R e5 to R e8 are independently hydrogen atoms, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a phenyl group.
- B is a single bond and has 1 to 10 carbon atoms.
- the aliphatic hydrocarbon groups having 1 to 5 carbon atoms represented by R e1 to Re 4 and Re 5 to Re 8 include methyl group, ethyl group and n-propyl group. Examples thereof include an isopropyl group, an n-butyl group and a t-butyl group. Among these, a methyl group and an ethyl group are preferable.
- R e1 and R e3 are methyl groups and R e2 and R e4 are ethyl groups.
- Examples of the alkylene group having 1 to 10 carbon atoms represented by D in the general formula (1) and B in the general formula (2) include a methylene group, a tetramethylene group, a hexamethylene group, a decamethylene group and the like. Among these, an alkylene group having 1 to 6 carbon atoms is preferable, an alkylene group having 2 to 6 carbon atoms is more preferable, and a hexamethylene group is further preferable.
- Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms represented by D include a phenylene group, a biphenylylene group, a naphthylene group and the like.
- Examples of the alkylidene group having 2 to 5 carbon atoms represented by B in the general formula (2) include an ethylidene group and an isopropylidene group. Among these, an isopropylidene group is preferable.
- R e1 to R e4 in the general formula (1) an aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferable, and a more preferable group is as described above.
- D in the general formula (1) an alkylene group having 1 to 10 carbon atoms is preferable, and a more preferable group is as described above.
- R e5 to R e8 in the general formula (2) a hydrogen atom and a phenyl group are preferable, and it is particularly preferable that R e5 and R e7 are hydrogen atoms and R e6 and R e8 are phenyl groups.
- B in the general formula (2) an alkylidene group having 2 to 5 carbon atoms is preferable, and a more preferable group is as described above.
- the compound represented by the following formula (3) or (4) is more preferable, and the compound represented by the following formula (3) is further preferable in consideration of the production cost. ..
- thermosetting resin composition contains the component (e)
- the content thereof is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin component. , 0.1 to 2 parts by mass is more preferable.
- it is 0.1 parts by mass or more, excellent heat resistance, flame retardancy and adhesiveness to a metal foil tend to be obtained, and when it is 10 parts by mass or less, heat resistance and aging stability are obtained. Properties and press formability tend to be difficult to deteriorate.
- thermosetting resin composition of the present embodiment is further referred to as (f) monoamine compound [hereinafter, referred to as (f) component. ] May or may not be contained.
- the thermosetting resin composition of the present embodiment can further improve the heat resistance by containing the component (f).
- a compound represented by the following general formula (f) is preferable.
- R f1 is independently an acidic substituent, a hydroxyl group, a carboxy group or a sulfonic acid group
- R f2 is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen. It is an atom.
- X is an integer of 1 to 5, and y is an integer of 0 to 4.
- the acidic substituent represented by R f1 is preferably a hydroxyl group or a carboxy group from the viewpoint of solubility and reactivity, and more preferably a hydroxyl group in consideration of heat resistance.
- x is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2, and further from the viewpoint of high heat resistance, low relative permittivity, high glass transition temperature, low thermal expansion and moldability. It is preferably 1.
- Examples of the alkyl group having 1 to 5 carbon atoms indicated by R f2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group and the like. ..
- the alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
- Examples of the halogen atom indicated by R f2 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
- y is an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, from the viewpoints of high heat resistance, low specific dielectric constant, high glass transition temperature, low thermal expansion and moldability. , More preferably 0 or 1, particularly preferably 0.
- x is an integer of 2 to 5
- a plurality of R f1s may be the same or different.
- y is an integer of 2 to 4, a plurality of R f2s may be the same or different.
- m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o-aminobenzenesulfonic acid, m-amino Benzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and the like can be mentioned.
- m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5-dihydroxyaniline are preferable from the viewpoint of solubility and synthetic yield.
- m-aminophenol and p-aminophenol are more preferable, and from the viewpoint of low thermal expansion, p-aminophenol is further preferable.
- thermosetting resin composition of the present embodiment contains the component (f), the content thereof is the resin component of the thermosetting resin composition from the viewpoint of reducing the coefficient of thermal expansion while maintaining heat resistance. 0.2 to 5 parts by mass is preferable with respect to 100 parts by mass.
- thermosetting resin composition of the present embodiment is optionally known as a thermoplastic resin, an organic filler, a flame retardant, a flame retardant aid, an ultraviolet absorber, or a peroxide to the extent that the thermosetting property is not impaired.
- Antioxidant, photopolymerization initiator, fluorescent whitening agent, adhesiveness improver and the like may be contained.
- thermoplastic resins include polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyamideimide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, and polyether ether.
- examples thereof include ketone resins, silicone resins, and tetrafluoroethylene resins.
- organic filler examples include resin fillers made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin and the like, resin fillers having a core-shell structure, and the like.
- Flame retardants include aromatic phosphoric acid ester compounds, phosphazene compounds, phosphinic acid esters, metal salts of phosphinic acid compounds, red phosphorus, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and itss.
- Phosphorus-based flame retardants such as derivatives; nitrogen-based flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate, melamine cyanurate; halogen-containing flame retardants containing bromine, chlorine and the like can be mentioned.
- the flame retardant aid include inorganic flame retardants such as antimony trioxide, sodium antimonate, ZnS, zinc borate, zinc sulfide, and zinc molybdate. These may be supported on a carrier such as talc, if necessary.
- a substance that functions as a flame retardant and a substance that functions as a flame retardant aid are not classified as an inorganic filler even if they are inorganic compounds, but are classified as a flame retardant or a flame retardant aid.
- the ultraviolet absorber examples include benzotriazole-based ultraviolet absorbers.
- the peroxide those that promote the reaction between the component (a) and the component (c) are preferable, and for example, organic peroxides such as ⁇ , ⁇ '-di (t-butylperoxy) diisopropylbenzene and the like are used. Can be mentioned.
- the thermosetting resin composition of the present embodiment contains a peroxide, the content thereof is not particularly limited, but is preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the resin component. , 0.3 to 2 parts by mass is more preferable, and 0.5 to 1.5 parts by mass is further preferable.
- antioxidant examples include a hindered phenol-based antioxidant, a hindered amine-based antioxidant and the like.
- the photopolymerization initiator examples include benzophenones, benzyl ketals, thioxanthone-based photopolymerization initiators, and the like.
- the fluorescent whitening agent examples include a fluorescent whitening agent of a stilbene derivative.
- the adhesiveness improving agent include urea compounds such as ureasilane and the coupling agent.
- thermosetting resin composition of the present embodiment may be in the state of a varnish in which each component is dissolved or dispersed in an organic solvent for use in the production of a prepreg or the like. That is, the varnish is also included in the thermosetting resin composition of the present embodiment.
- organic solvent used for the varnish include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; butyl acetate and propylene.
- Ester-based solvents such as glycol monomethyl ether acetate; Ether-based solvents such as tetrahydrofuran; Aromatic solvents such as toluene, xylene and mesitylene; Nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; Examples include a sulfur atom-containing solvent.
- the organic solvent one type may be used alone, or two or more types may be used in combination.
- methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether are preferable from the viewpoint of solubility, and methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity.
- the solid content concentration of the varnish is preferably 40 to 90% by mass, more preferably 50 to 80% by mass. When the solid content concentration of the varnish is within the above range, the coatability can be kept good and a prepreg having an appropriate amount of the resin composition adhered can be obtained.
- the prepreg of the present embodiment contains the thermosetting resin composition of the present embodiment, and more specifically, contains a B-staged thermosetting resin composition.
- the prepreg of the present embodiment can be produced, for example, by impregnating a fiber base material with the thermosetting resin composition of the present embodiment and forming it into a B stage by heating or the like.
- B-stage formation means to bring the B-stage state as defined in JIS K6900 (1994), and is also referred to as semi-curing.
- the fiber base material well-known materials used for various laminated boards for electrical insulating materials can be used.
- the material examples include inorganic fibers such as E glass, S glass, low dielectric glass, and Q glass; organic fibers such as low dielectric glass polyimide, polyester, and tetrafluoroethylene; and mixtures thereof.
- inorganic fibers such as E glass, S glass, low dielectric glass, and Q glass
- organic fibers such as low dielectric glass polyimide, polyester, and tetrafluoroethylene
- low-dielectric glass and Q glass are preferable from the viewpoint of obtaining a base material having excellent dielectric properties.
- These fiber base materials have shapes such as woven fabrics, non-woven fabrics, robinks, chopped strand mats, and surfaced mats, and the materials and shapes are selected according to the intended use and performance of the molded product.
- the fiber base material can be used alone or in combination of two or more kinds of materials and shapes, if necessary.
- As the thickness of the fiber base material for example, one having a thickness of about 0.03 to 0.5 mm can be used.
- these fiber base materials those surface-treated with a silane coupling agent or the like or those subjected to mechanical opening treatment are suitable from the viewpoints of heat resistance, moisture resistance, processability and the like.
- the prepreg of the present embodiment can be produced by the following method.
- the thermosetting resin has a target of preferably 20 to 90% by mass of the amount of the thermosetting resin composition adhered to the fiber base material (the content of the thermosetting resin composition in the prepreg).
- the fiber substrate is impregnated with the composition.
- the prepreg can be obtained by heating and drying at a temperature of 100 to 200 ° C. for 1 to 30 minutes to form a B stage.
- the prepreg of the present embodiment has excellent desmear resistance, even if a prepreg having a thickness of 40 to 300 ⁇ m or even a prepreg having a thickness of 40 to 200 ⁇ m is used, the amount of weight change before and after the desmear treatment can be suppressed to a small value. ing.
- the thickness is the thickness of the prepreg after heating and drying.
- the laminated board of this embodiment is a laminated board containing the prepreg of this embodiment.
- the laminated board of this embodiment is obtained by laminating and molding the prepreg of this embodiment. Specifically, one prepreg of the present embodiment is prepared, or two to 20 prepregs are prepared, and metal foils such as copper and aluminum are arranged on one side or both sides of the prepreg. It can be manufactured by. According to the manufacturing method, a laminated board having an insulating layer (the insulating layer is C-staged) formed by using the prepreg of the present embodiment and metal foils arranged on one side or both sides thereof is formed. can get.
- the metal foil is not particularly limited as long as it is used for electrical insulating material.
- the laminated board in which the metal foil is arranged on one side or both sides of the laminated board of the present embodiment is particularly referred to as a metal-clad laminated board.
- C-stage formation means to make the C-stage state as defined in JIS K6900 (1994).
- the method of the laminated board for the electric insulating material and the multi-layer board can be applied, and a multi-stage press, a multi-stage vacuum press, continuous molding, an autoclave molding machine, etc. are used.
- a laminated board can also be manufactured by combining the prepreg of the present embodiment and the wiring board for the inner layer and laminating and molding the prepreg.
- the printed wiring board of the present embodiment is a printed wiring board obtained by forming a circuit on the laminated board or the metal-clad laminated board of the present embodiment.
- the circuit forming method include known methods such as a subtractive method, a full additive method, a semi-additive method (SAP: Semi Adaptive Process), and a modified semi-additive method (m-SAP: modified Semi Adaptive Process).
- SAP Semi Adaptive Process
- m-SAP modified Semi Adaptive Process
- a plurality of laminated plates having a circuit formed may be laminated with the prepreg of the present embodiment sandwiched between them, and then heat-pressed to form multiple layers.
- a multilayer printed wiring board can be manufactured by forming through holes or blind via holes by drilling or laser processing and forming interlayer wiring by plating or conductive paste.
- the present disclosure also provides a semiconductor package containing the printed wiring board and the semiconductor element of the present embodiment.
- a semiconductor package can be manufactured by mounting a semiconductor element such as a semiconductor chip or a memory at a predetermined position on the multilayer printed wiring board and sealing the semiconductor element with a sealing resin or the like.
- the copper foil is removed by immersing the copper-clad laminate manufactured in each example in a copper etching solution, and the evaluation substrate is 5 mm (X direction) x 5 mm square (Y direction) by cutting. Was produced. The cutting was performed in a state where the cut surface was along the glass fiber direction.
- thermomechanical analysis was performed by a compression method using a TMA test apparatus (TMAQ400EM manufactured by TA Instruments Japan Co., Ltd.). The measurement direction of the coefficient of thermal expansion was the X direction. After mounting the evaluation substrate on the apparatus, the temperature is raised to 260 ° C. at a temperature rising rate of 10 ° C./min, the temperature is lowered to 10 ° C.
- FIG. 2 shows an SEM photograph of the surface of the substrate after the desmear treatment in Example 4.
- modified maleimide resin (A) which is a component (a)
- a reaction vessel having an internal volume of 2 L equipped with a thermometer, a stirrer, and a moisture quantifier with a reflux condenser
- 119 parts by mass (solid content equivalent amount) ((a2') component) of the azomethine-modified siloxane-containing solution 2, 161 parts by mass of 2-bis [4- (4-maleimidephenoxy) phenyl] propane (component (a1)) and 376 parts by mass of propylene glycol monomethyl ether were added and reacted at 120 ° C. for 4 hours to modify a modified maleimide resin [hereinafter, modified. It is called maleimide resin (A-1). ]
- a containing solution was obtained.
- a-1 Modified maleimide resin (A-1) synthesized in Synthesis Example 1 a-2: Polyphenylmethanemaleimide, component (a1), melting point 70 to 145 ° C, see chemical structural formula below (N1 is an integer from 1 to 10.)
- b-1 Fused spherical silica (small) (average particle size: 50 nm, maximum peak in frequency distribution exists at particle size 30 nm)
- b-2 Fused spherical silica (medium) (average particle size: 0.3 to 0.8 ⁇ m, maximum peak in frequency distribution exists at particle size 0.6 ⁇ m)
- b-3 Fused spherical silica (large) (trade name: SO-C4, manufactured by Admatex Co., Ltd., average particle size: 0.9 to 1.2 ⁇ m, maximum peak in frequency distribution is 1.0 ⁇ m.
- Example 700 g is added to 300 g of a methyl isobutyl ketone solution containing 7 g of KBM-903 (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd., 3-aminopropyltrimethoxysilane) with stirring, and methyl of molten spherical silica is added.
- KBM-903 trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd., 3-aminopropyltrimethoxysilane
- An isobutyl solution was prepared and used as the b-3 component.
- the average particle size is the particle size (volume average particle size) of a point corresponding to a volume of 50% when the cumulative frequency distribution curve based on the particle size is obtained with the total volume of particles as 100%.
- c-5 "TA-G", trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd., (c2) component, refer to the following chemical structural formula c-6: "TAIC”, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd., (C2) component, refer to the following chemical structural formula c-7: "DD-1", trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd., (c2) component, refer to the following chemical structural formula (In the formula, R c2 is an aliphatic hydrocarbon group having 2 to 18 carbon atoms which may contain at least one selected from the group consisting of an ether group and a hydroxyl group.)
- Diamine compound 4,4'-diaminodiphenyl sulfone
- thermosetting resin composition of the present embodiment a laminated board having excellent low thermal expansion property and desmear resistance can be obtained, so that a high-density and high-multilayer printed wiring board can be manufactured. It is suitably used for printed wiring boards of electronic devices used such as computers and information device terminals that process a large amount of data at high speed. In particular, it can also be used for printed wiring boards of tablet-type personal computers and notebook-type personal computers, which are in great demand for thinning.
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Abstract
Description
さらに、タブレット型パソコン及びノート型パソコンでは製品のさらなる薄型化の要求があり、半導体用パッケージ基板の薄型化が必要となっている。しかし、半導体用パッケージ基板を薄型にするためにはプリプレグを薄型化した場合、プリプレグにCO2レーザ加工等によってスルーホールを形成する際に生じるスミアの除去(デスミア)時に、ガラスクロス及び無機充填材等が露出し易くなって製品の信頼性が低下する傾向にある。特に、CO2レーザ加工はドリル加工に比べてスミアの発生量が多いため、該スミアを十分に除去する必要があり、それゆえ、プリプレグ、ひいては積層板には、より一層の耐デスミア性の向上が求められる。
本実施形態の一態様は、下記[1]~[14]に関する。
さらに、(c)少なくとも2個の不飽和脂肪族炭化水素基を有する化合物を含有してなる、熱硬化性樹脂組成物。
[2]前記(a)成分が、(a1)少なくとも2個のN-置換マレイミド基を有するマレイミド化合物と(a2)少なくとも2個の1級アミノ基を有するシリコーン化合物との反応物を含有する、上記[1]に記載の熱硬化性樹脂組成物。
[3]前記(b)成分の体積基準の粒子径分布のピークの極大が、少なくとも、0.01μm以上1.0μm未満の範囲に存在する、上記[1]又は[2]に記載の熱硬化性樹脂組成物。
[4]前記(b)成分の体積基準の粒子径分布のピークの極大が、0.01μm以上0.1μm未満の範囲と0.1μm以上10μm以下の範囲の両方に存在する、上記[1]~[3]のいずれかに記載の熱硬化性樹脂組成物。
[5]前記(c)成分が、少なくとも3個の不飽和脂肪族炭化水素基を有する化合物である、上記[1]~[4]のいずれかに記載の熱硬化性樹脂組成物。
[6]前記(c)成分が、(c1)少なくとも2個の不飽和脂肪族炭化水素基を有し、且つ、芳香族炭化水素基を有する化合物である、上記[1]~[4]のいずれかに記載の熱硬化性樹脂組成物。
[7]前記(c)成分が、(c2)少なくとも2個の不飽和脂肪族炭化水素基を有し、且つ、下記一般式(c2-1)又は下記一般式(c2-2)のいずれかの構造を有する化合物である、上記[1]~[4]のいずれかに記載の熱硬化性樹脂組成物。
(上記式中、*は他の基への連結部位であることを示す。)
[8]前記(c)成分が有する不飽和脂肪族炭化水素基が、ビニル基、イソプロペニル基、1-プロペニル基、アリル基、1-メチルアリル基及び3-ブテニル基からなる群から選択される少なくとも1種である、上記[1]~[7]のいずれかに記載の熱硬化性樹脂組成物。
[9]上記[1]~[8]のいずれかに記載の熱硬化性樹脂組成物を含有してなるプリプレグ。
[10]厚みが40~300μmである、上記[9]に記載のプリプレグ。
[11]上記[9]又は[10]に記載のプリプレグを含有してなる積層板。
[12]上記[11]に記載の積層板の片面又は両面に金属箔が配置された金属張り積層板。
[13]上記[11]に記載の積層板又は上記[12]に記載の金属張り積層板に回路形成して得られる、プリント配線板。
[14]上記[13]に記載のプリント配線板及び半導体素子を含有する半導体パッケージ。
本明細書において、例えば、「10以上」という記載は、10及び10を超える数値を意味し、数値が異なる場合もこれに準ずる。また、例えば、「10以下」という記載は、10及び10未満の数値を意味し、数値が異なる場合もこれに準ずる。
また、本明細書に例示する各成分及び材料は、特に断らない限り、1種を単独で使用してもよいし、2種以上を併用してもよい。本明細書において、組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。
なお、本明細書において、「樹脂成分」とは、(a)成分及び(c)成分、並びに必要に応じて使用する(d)成分、(f)モノアミン化合物、及びその他の任意で使用する樹脂のことであり、(b)無機充填材、(e)硬化促進剤及び添加剤等は含まれない。
本明細書において、「固形分」とは、水分、後述する溶媒等の揮発する物質以外の樹脂組成物中の成分のことをいう。すなわち、固形分は、25℃付近の室温で液状、水飴状又はワックス状のものも含み、必ずしも固体であることを意味するものではない。
本明細書における記載事項を任意に組み合わせた態様も本実施形態に含まれる。
本実施形態の熱硬化性樹脂組成物は、(a)少なくとも1個のN-置換マレイミド基を有するマレイミド化合物[以下、(a)成分と称することがある。]及び(b)無機充填材[以下、(b)成分と称することがある。]を含有してなり、且つ、前記(b)無機充填材の含有量が熱硬化性樹脂組成物総量に対して53~65体積%である熱硬化性樹脂組成物であって、さらに、(c)少なくとも2個の不飽和脂肪族炭化水素基を有する化合物[以下、(c)成分と称することがある。]を含有してなる、熱硬化性樹脂組成物である。
前記(a)成分及び前記(b)成分を含有してなる熱硬化性樹脂組成物において、前記(b)成分の含有量を前記範囲に高めることによって低熱膨張性を向上させながら、熱硬化性樹脂組成物に前記(c)成分を含有させることにより、耐デスミア性も向上させることができた。
以下、本実施形態の熱硬化性樹脂組成物が含有する各成分について詳述する。
本実施形態の熱硬化性樹脂組成物は、(a)成分を含有することにより、耐熱性、低熱膨張性に優れたものとすることができる。但し、低熱膨張性に対する市場の要求は年々厳しくなっており、(a)成分を用いるだけでは低熱膨張性は不十分であり、前述の通り、本実施形態ではさらに(b)成分の含有量を高めることで、優れた低熱膨張性を発現可能としている。
(a)成分は、耐熱性及び低熱膨張性の観点から、(a1)少なくとも2個のN-置換マレイミド基を有するマレイミド化合物[以下、(a1)成分と称することがある。]を含有することが好ましく、耐熱性、低熱膨張性、及び金属箔との接着性の観点から、前記(a1)成分と(a2)少なくとも2個の1級アミノ基を有するシリコーン化合物[以下、(a2)成分と称することがある。]との反応物[以下、変性マレイミド樹脂(A)と称することがある。]を含有することがより好ましい。
また、(a)成分は、前記(a1)成分と前記変性マレイミド樹脂(A)とを含有することも好ましい。
前記(a1)成分としては、下記一般式(a1-1)で表されるマレイミド化合物がより好ましい。
(式中、Ra2は、各々独立に、炭素数1~5の脂肪族炭化水素基又はハロゲン原子である。Xa2は、炭素数1~5のアルキレン基、炭素数2~5のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボニルオキシ基、ケト基、単結合又は下記一般式(a1-3’)で表される基である。q1は、各々独立に、0~4の整数である。*は結合部位を表す。)
(式中、Ra3は、各々独立に、炭素数1~5の脂肪族炭化水素基又はハロゲン原子である。Xa3は、炭素数1~5のアルキレン基、炭素数2~5のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボニルオキシ基、ケト基、又は単結合である。r1は、各々独立に、0~4の整数である。*は結合部位を表す。)
前記一般式(a1-2)中、Ra1が表す炭素数1~5の脂肪族炭化水素基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、t-ブチル基、n-ペンチル基等が挙げられる。また、ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。
Ra1としては、脂肪族炭化水素基が好ましい。
p1は、0~4の整数であり、入手容易性の観点から、好ましくは0~2の整数、より好ましくは0である。p1が2以上の整数である場合、複数のRa1同士は同一であっても異なっていてもよい。
Ra2としては、炭素数1~5の脂肪族炭化水素基が好ましい。
Xa2が表す炭素数1~5のアルキレン基としては、メチレン基、1,2-ジメチレン基、1,3-トリメチレン基、1,4-テトラメチレン基、1,5-ペンタメチレン基等が挙げられる。該アルキレン基としては、好ましくは炭素数1~3のアルキレン基、より好ましくはメチレン基である。
Xa2が表す炭素数2~5のアルキリデン基としては、エチリデン基、プロピリデン基、イソプロピリデン基、ブチリデン基、イソブチリデン基、ペンチリデン基、イソペンチリデン基等が挙げられる。これらの中でも、イソプロピリデン基が好ましい。
Xa2としては、前記選択肢の中でも、炭素数1~5のアルキレン基、炭素数2~5のアルキリデン基、一般式(a1-3’)で表される基が好ましく、一般式(a1-3’)で表される基がより好ましい。
q1は、各々独立に、0~4の整数であり、入手容易性の観点から、好ましくは0~2の整数、より好ましくは0又は2である。複数のRa2同士は、それぞれ同一であっても異なっていてもよい。
Xa3が表す炭素数1~5のアルキレン基、炭素数2~5のアルキリデン基としては、Xa2が表す炭素数1~5のアルキレン基、炭素数2~5のアルキリデン基と同じものが挙げられる。
Xa3としては、上記選択肢の中でも、好ましくは炭素数2~5のアルキリデン基、より好ましくはイソプロピリデン基である。
r1は、0~4の整数であり、入手容易性の観点から、好ましくは0~2の整数、より好ましくは0である。複数のRa3同士は、それぞれ同一であっても異なっていてもよい。
ここで、前記変性マレイミド樹脂(A)の原料として使用する(a1)成分としては、前記一般式(a1-1)中のXa1が前記一般式(a1-3)で表されるマレイミド化合物が好ましく、特に、前記一般式(a1-3)においてXa2が前記一般式(a1-3’)で表されるマレイミド化合物がより好ましい。
前記一般式(a1-6)中、Ra4が表す炭素数1~5の脂肪族炭化水素基、ハロゲン原子としては、前記一般式(a1-2)中のRa1が表すそれらと同じものが挙げられ、Ra4の好ましい炭素数1~5の脂肪族炭化水素基及びハロゲン原子もRa1の場合と同じである。
u1は、1~8の整数であり、好ましくは1~3の整数、より好ましくは1である。
ここで、前記(a2)成分と反応させずに使用する(a1)成分としては、前記変性マレイミド樹脂(A)の有機溶剤に対する溶解性を高める観点から、前記一般式(a1-1)中のXa1が前記一般式(a1-4)で表されるマレイミド化合物(つまりポリフェニルメタンマレイミド)が好ましい。
変性マレイミド樹脂(A)を製造するために前記(a1)と反応させる(a2)成分としては、少なくとも一方の分子末端にアミノ基を有するシリコーン化合物が好ましく、分子両末端にアミノ基を有するシリコーン化合物がより好ましい。さらに、側鎖にアミノ基を有するシリコーン化合物であってもよく、側鎖及び少なくとも一方の分子末端にアミノ基を有するシリコーン化合物であってもよい。これらの中でも、(a2)成分としては分子両末端にアミノ基を有するシリコーン化合物が特に好ましく、このようなシリコーン化合物としては、下記一般式(a2-1)で表されるアミノ変性シリコーン化合物が好ましく挙げられる。
Ra21で表される置換フェニル基における置換基としては、アルキル基、アルケニル基、アルキニル基等が挙げられ、これらの中でも、アルキル基が好ましい。アルキル基としては、前記と同様のものが好ましく挙げられる。
Ra21で表される基の中でも、他の樹脂との溶解性の観点から、フェニル基又はメチル基が好ましく、メチル基がより好ましい。
Ra22又はRa23で表される有機基としては、アルキレン基、アルケニレン基、アルキニレン基、アリーレン基、エーテル基又はこれらが組み合わされた連結基が挙げられる。これらの中でも、置換又は無置換のアルキレン基、置換又は無置換のアリーレン基が好ましく、置換又は無置換のアルキレン基がより好ましい。該アルキレン基としては、メチレン基、エチレン基、トリメチレン基等が挙げられ、トリメチレン基が好ましい。該アルキレン基の置換基としては、特に制限されるものではないが、炭素数6~10のアリール基等が挙げられる。該アリーレン基としては、フェニレン基、ナフチレン基等が挙げられる。該アリーレン基の置換基としては、特に制限されるものではないが、炭素数1~5のアルキル基等が挙げられる。
Ra22及びRa23は、単結合であってもよいし、有機基であってもよいが、有機基であることが好ましい。
(a2)成分は、1種を単独で使用してもよいし、2種以上を併用してもよい。
市販品の中でも、低吸水率の観点から、X-22-161A、X-22-161B、KF-8012、KF-8008、X-22-1660B-3、BY-16-853B、XF42-C5379が好ましく、低熱膨張性の観点から、X-22-161A、X-22-161B、KF-8012、XF42-C5379が好ましい。
さらに、(a2)成分としては、低熱膨張率の観点から、アゾメチン基(-N=CH-)を有しているものが好ましく、芳香族アゾメチン基を有しているものがより好ましく、ジアルデヒド化合物と反応させて得られるアゾメチン変性シロキサン[以下、アゾメチン変性シロキサン(a2’)又は(a2’)成分と称することがある。]がさらに好ましい。ここで、芳香族アゾメチン基とは、アゾメチン基(-N=CH-)に少なくとも1つの芳香族基(好ましくは芳香族炭化水素基)が結合したものをいう。
前記ジアルデヒド化合物としては、脂肪族ジアルデヒド化合物、芳香族ジアルデヒド化合物等が挙げられる。これらの中でも、芳香族ジアルデヒド化合物が好ましい。該芳香族ジアルデヒド化合物は、芳香族炭化水素基を有しており、その限りにおいて、脂肪族炭化水素基を併せ持っていてもよい。例えば、分子内に芳香族炭化水素基-脂肪族炭化水素基-芳香族炭化水素基という構造を有している場合も、芳香族アルデヒド化合物に含まれる。
アゾメチン変性シロキサン(a2’)の製造方法に特に制限はなく、例えば、始めに、前記一般式(a2-1)で表されるアミノ変性シリコーン化合物と、前記ジアルデヒド化合物とを有機溶媒中で脱水縮合反応させることにより製造できる。ここで、前記一般式(a2-1)で表されるアミノ変性シリコーン化合物と前記ジアルデヒド化合物の使用量は、例えば、前記一般式(a2-1)で表されるアミノ変性シリコーン化合物の第一級アミノ基数〔アミノ変性シリコーン化合物の使用量/アミノ変性シリコーン化合物の第一級アミノ基当量〕が、ジアルデヒド化合物のアルデヒド基数〔ジアルデヒド化合物の使用量/ジアルデヒド化合物のアルデヒド基当量〕の1.1倍以上になることを目標にして調整することが好ましく、1.5~5倍になることを目標にして調整してもよく、2~4倍になることを目標にして調整してもよい。前記比率が1.1倍以上になることを目標にして調整することにより、反応を十分に進行させ、分子両末端にアミノ基を有する状態となる。
変性マレイミド樹脂(A)の製造方法に特に制限はないが、前記(a1)成分が持つマレイミド基の炭素-炭素二重結合へ前記(a2)成分が持つアミノ基を付加反応させることで変性マレイミド樹脂(A)を製造することができる。
(a)成分として変性マレイミド樹脂(A)を製造しておき、それを用いることで、熱硬化性樹脂組成物中の樹脂の分子量を制御し易くなり、低熱膨張性及び弾性率を向上させ易くなる傾向にある。なお、後述する(f)モノアミン化合物を一緒に反応させて変性マレイミド樹脂(A)を製造してもよいし、該(f)モノアミン化合物は、変性マレイミド樹脂(A)の製造に使用しなくてもよい。
変性マレイミド樹脂(A)の製造は、有機溶媒中で加熱保温しながら行なうことが好ましい。反応温度は、70~200℃が好ましく、70~150℃がより好ましく、100~130℃がさらに好ましい。反応時間は、0.1~10時間が好ましく、1~6時間がより好ましい。
本実施形態の熱硬化性樹脂組成物における(a)成分の含有量は、特に制限されるものではないが、熱硬化性樹脂組成物中の樹脂成分100質量部に対して、30~99質量部が好ましく、35~90質量部がより好ましく、40~85質量部がさらに好ましく、45~80質量部が特に好ましい。
なお、(a)成分が前記(a1)成分と、前記変性マレイミド樹脂(A)とを含有する場合、(a1)成分及び変性マレイミド樹脂(A)それぞれの含有量は、特に制限されるものではないが、熱硬化性樹脂組成物中の樹脂成分100質量部に対して、いずれも、10~60質量部が好ましく、15~55質量部がより好ましく、20~50質量部がさらに好ましく、20~40質量部が特に好ましい。
本実施形態の熱硬化性樹脂組成物は、(b)無機充填材を熱硬化性樹脂組成物総量に対して53~65体積%含有することで、低熱膨張性が得られる。低熱膨張性の観点から、(b)無機充填材の含有量は、54~62体積%が好ましく、55~60体積%がより好ましく、56~59体積%がさらに好ましい。
(b)成分の含有量を熱硬化性樹脂組成物総量に対して53体積%以上にすると、低熱膨張性には優れる一方で、耐デスミア性が低下することが判明したが、前述の通り、耐デスミア性については、後述の(c)成分を含有させることによって解決した。また、(b)成分の含有量を前記の通りに高めることで、プリプレグ及び積層板が高弾性化し、そりの低減効果も期待できる。
ところで、(b)成分の含有量を熱硬化性樹脂組成物総量に対して53体積%以上にすることは、一般的にはプリプレグにカスレが生じる原因となるため、容易なことではない。そこで、(b)成分の含有量を前記範囲へ高める方法として、ナノフィラーを使用する方法を採用することが好ましい。換言すると、本実施形態においては、前記(b)成分の粒子径分布のピークの極大が、少なくとも、0.01μm以上0.1μm未満の範囲に存在する態様が好ましい。さらには、前記(b)成分の体積基準の粒子径分布のピークの極大が、0.01μm以上0.1μm未満の範囲と0.1μm以上10μm以下の範囲の両方に存在する態様がより好ましい。このような態様とすることで、(b)成分の含有量を熱硬化性樹脂組成物総量に対して53体積%以上にすることが可能となる。
ここで、本開示において、粒子径分布は、体積基準の頻度分布である。また、粒子径分布のピークの極大とは、頻度として表した粒子径分布(体積基準)におけるピークにおいて、山になっているピークにおいて頻度が極大値となる位置のことであり、図1を用いて説明すると、極大(B1)及び極大(B2)のことである。当該測定は、レーザ回折散乱法を用いた粒度分布測定装置で行なう。
これらの中でも、誘電特性、耐熱性及び低熱膨張性の観点から、シリカが好ましい。シリカとしては、例えば、湿式法で製造された含水率の高い沈降シリカと、乾式法で製造された結合水等をほとんど含まない乾式法シリカが挙げられる。乾式法シリカとしては、さらに、製造法の違いにより、破砕シリカ、フュームドシリカ、溶融球状シリカ等に分類される。これらの中でも、低熱膨張性及び樹脂に充填した際の流動性の観点から、溶融球状シリカが好ましい。
カップリング剤としては、シラン系カップリング剤、チタネート系カップリング剤、シリコーンオリゴマー等が挙げられる。これらの中でも、シラン系カップリング剤が好ましい。該シランカップリング剤としては、エポキシシラン系カップリング剤、アミノシラン系カップリング剤、ビニルシラン系カップリング剤、フェニルシラン系カップリング剤、アルキルシラン系カップリング剤、アルケニルシラン系カップリング剤、アルキニルシラン系カップリング剤、ハロアルキルシラン系カップリング剤、シロキサン系カップリング剤、ヒドロシラン系カップリング剤、シラザン系カップリング剤、アルコキシシラン系カップリング剤、クロロシラン系カップリング剤、(メタ)アクリルシラン系カップリング剤、イソシアヌレートシラン系カップリング剤、ウレイドシラン系カップリング剤、メルカプトシラン系カップリング剤、スルフィドシラン系カップリング剤、イソシアネートシラン系カップリング剤等が挙げられる。これらの中でも、アミノシラン系カップリング剤がより好ましい。
(b1)無機充填材及び(b2)無機充填材は、それぞれ、1種を単独で使用してもよいし、本実施形態の効果を損なわない限りにおいて、それぞれ、2種以上を併用してもよい。
粒子径分布範囲(b2)は、低熱膨張性、弾性率及び成形性の観点から、好ましくは0.3μm以上8μm以下、より好ましくは0.5μm以上5μm以下、さらに好ましくは0.5μm以上3μm以下、特に好ましくは0.5μm以上1.5μm以下である。
なお、上記の粒子径の「差」は絶対値である。但し、該粒子径の差は、粒子径分布範囲(b1)に存在するピークの極大が2つ以上ある場合、又は粒子径分布範囲(b2)に存在するピークの極大が2つ以上ある場合は、それぞれの範囲において最も大きなピーク同士の差を指す。
前記(b2)無機充填材の平均粒子径を0.1μm以上にすることで、熱硬化性樹脂組成物に(b2)無機充填材を高充填した際の流動性を良好に保ち易い傾向があり、前記(b2)無機充填材の平均粒子径を10μm以下にすることで、粗大粒子の混入確率を減らし、粗大粒子起因の不良の発生を抑制し易い傾向がある。さらに、前記平均粒子径を有する(b1)無機充填材を併用することで、熱硬化性樹脂組成物の流動性の向上及び無機充填材の高充填化が可能となる傾向にある。
ここで、本明細書において平均粒子径とは、粒子の全体積を100%として粒子径による累積度数分布曲線を求めたとき、体積50%に相当する点の粒子径(体積平均粒子径)のことであり、レーザ回折散乱法を用いた粒度分布測定装置で測定する。
当然のことながら、(b)無機充填材が前述の好ましいもの、つまりシリカ(溶融球状シリカ)であっても、上記同様の含有量が好ましい。
本実施形態では、前記(b)成分の含有量を熱硬化性樹脂組成物総量に対して53体積%以上にすることで低熱膨張性に優れる一方で、そのままでは耐デスミア性が低下することが判明したが、該(c)成分を含有させることによって耐デスミア性も向上した。該(c)成分を含有させることによって耐デスミア性も向上した正確な理由は不明ではあるが、次の様に推察する。該(c)成分は、例えばジアミン化合物とは異なり、マレイミド基が持つ炭素-炭素二重結合との反応の際に第二級アミノ基を生じず、且つ、未反応のマレイミド基とディールスアルダー反応することによって、酸化に強い構造を形成しているものと考える。第二級アミノ基が生じないことによって、耐デスミア性を低下させずに済んでおり、且つ、ディールスアルダー反応で酸化に強い構造を形成したことで、耐デスミア性が向上するに至ったものと推察する。
(c)成分は、1種を単独で使用してもよいし、2種以上を併用してもよい。
また、(c)成分が有する不飽和脂肪族炭化水素基としては、特に制限されるものではないが、ラジカル反応し得る不飽和脂肪族炭化水素基であることが好ましく、ビニル基、イソプロペニル基、1-プロペニル基、アリル基、1-メチルアリル基、3-ブテニル基等からなる群から選択される少なくとも1種であることがより好ましい。これらの中でも、耐デスミア性の観点から、炭素数2~10の不飽和脂肪族炭化水素基が好ましく、炭素数2~5の不飽和脂肪族炭化水素基がより好ましく、1-プロペニル基、アリル基がさらに好ましい。なお、本開示においては、マレイミド基及び(メタ)アクリロイル基等の様に、一部に不飽和脂肪族炭化水素基を有しているが、その基全体として見たときに不飽和脂肪族炭化水素基とは言えない基は、(c)成分における「不飽和脂肪族炭化水素基」に含まれないこととする。
前記(c1)成分としては、1種を単独で使用してもよいし、2種以上を併用してもよい。前記(c2)成分としては、1種を単独で使用してもよいし、2種以上を併用してもよい。
なお、(c)成分としては、(c1)成分及び(c2)成分からなる群から選択される少なくとも1種を含んでいることが好ましく、(c1)成分を含む態様も好ましく、(c2)成分を含む態様も好ましい。
(上記式中、*は他の基への連結部位であることを示す。該*は、特に制限されるものではないが、不飽和脂肪族炭化水素基に直結している態様が、好ましい態様のうちの1つである。)
なお、該芳香族炭化水素基は置換基を有していてもよく、該置換基としては、特に制限されるものではないが、ヒドロキシル基、アルコキシル基等が挙げられる。
(c1)成分の具体例としては、以下の化合物が挙げられる。
(式中、Rc1~Rc3は、それぞれ独立に、有機基である。mc1は、それぞれ独立に、0又は1である。nc1及びnc2はいずれも、鍵括弧で囲まれた部位の繰り返し単位数を表し、それぞれ独立に、1~100である。)
(式中、Rc4~Rc7は、それぞれ独立に、有機基である。mc2及びmc3は、それぞれ独立に、0又は1である。nc3~nc6はいずれも、鍵括弧で囲まれた部位の繰り返し単位数を表し、それぞれ独立に、1~100である。)
(式中、Rc8及びRc9は、それぞれ独立に、有機基である。nc7~nc10は、いずれも丸括弧で囲まれた部位の繰り返し単位数を表し、それぞれ独立に、1~100である。)
Rc1~Rc9が表す有機基は、いずれも、前記選択肢の中でも嵩高い有機基であることが好ましく、炭素数4~20のアルキル基、環形成炭素数6~18のアリール基、環形成炭素数6~18のアラルキル基、炭素数5~18の脂環式炭化水素基がより好ましく、炭素数4~20のアルキル基、環形成炭素数6~18のアラルキル基、炭素数5~18の脂環式炭化水素基がさらに好ましい。
なお、1分子中に複数のRc1が存在する場合、複数のRc1はそれぞれ同一であってもよいし、異なっていてもよいし、同一のものと異なっているものとが混在していてもよい。Rc2~Rc9についてもこれと同様のことがいえる。
mc1~mc3は、それぞれ独立に、0及び1のいずれでもよい。
nc1~nc10としては、それぞれ独立に、1~100が好ましく、3~30がより好ましい。
(上記式中、Rc2は、エーテル基及びヒドロキシル基からなる群から選択される少なくとも1種を含んでいてもよい炭素数2~18の脂肪族炭化水素基である。)
(式中、pc1はメチレン基の繰り返し単位数を表し、2~18の整数である。pc2はオキシエチレン基の繰り返し単位数を表し、0又は1である。*は結合部位である。)
前記pc2は、0であってもよいし、1であってもよいが、好ましくは1である。
本実施形態の熱硬化性樹脂組成物における(c)成分の含有量は、特に制限されるものではないが、低熱膨張性及び耐デスミア性の観点から、前記(a)成分のマレイミド基の数に対する(c)成分中の炭素-炭素二重結合の数の比率[炭素-炭素二重結合の数/マレイミド基の数]が0.4~0.9になることを目標として調整することが好ましい。
例えば、(c)成分の含有量は、熱硬化性樹脂組成物の樹脂成分100質量部に対して2~80質量部が好ましく、5~65質量部がより好ましく、8~45質量部がさらに好ましい。特に、(c)成分として前記(c1)成分を含有する場合、(c1)成分の含有量は、低熱膨張性及び耐デスミア性の観点から、熱硬化性樹脂組成物の樹脂成分100質量部に対して10~80質量部が好ましく、15~65質量部がより好ましく、25~45質量部がさらに好ましく、25~40質量部が特に好ましい。また、(c)成分として前記(c2)成分を含有する場合、(c2)成分の含有量は、低熱膨張性及び耐デスミア性の観点から、熱硬化性樹脂組成物の樹脂成分100質量部に対して2~65質量部が好ましく、2~40質量部がより好ましく、2~25質量部がさらに好ましく、5~20質量部が特に好ましく、8~18質量部が最も好ましい。
本実施形態の熱硬化性樹脂組成物は、さらに(d)熱硬化性樹脂[以下、(d)成分と称することがある。]を含有していてもよい。本実施形態の熱硬化性樹脂組成物が(d)成分を含有することにより、特に、銅箔等の金属箔との接着性を向上させることができる。但し、本実施形態の熱硬化性樹脂組成物は(d)熱硬化性樹脂を含有していなくてもよい。
なお、該(d)成分には前記(a)成分は含まれないものとする。
また、(d)熱硬化性樹脂としては、成形性の観点から、150℃におけるICI粘度が、好ましくは1.0Pa・s以下、より好ましくは0.5Pa・s以下、さらに好ましくは0.3Pa・s以下、特に好ましくは0.2Pa・s以下の熱硬化性樹脂を選択するのがよい。ここで、ICI粘度は、ICI粘度計として知られる高せん断速度を測定するもので、コーンプレート型粘度計で測定される粘度である。
これらの中でも、成形性の観点から、150℃におけるICI粘度が1.0Pa・s以下(より好ましくは前述の通りである。)のエポキシ樹脂が好ましく、ナフタレン骨格含有ノボラック型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂がより好ましく、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂がさらに好ましく、ナフタレン型エポキシ樹脂が特に好ましい。
本実施形態の熱硬化性樹脂組成物が(d)熱硬化性樹脂を含有する場合、その含有量は、耐熱性、低熱膨張性、金属箔との接着性の観点から、熱硬化性樹脂組成物の樹脂成分100質量部に対して、5~50質量部が好ましく、10~40質量部がより好ましく、15~40質量部がさらに好ましい。
本実施形態の熱硬化性樹脂組成物は、(e)硬化促進剤[以下、(e)成分と称することがある。]を含有していてもよい。熱硬化性樹脂組成物が(e)成分を含有することによって、耐熱性、難燃性及び金属箔との接着性等がより向上する。
(e)成分としては、イミダゾール類及びその誘導体;ホスフィン類及びホスホニウム塩、第三級ホスフィンとキノン類との付加物等の有機リン系化合物;第二級アミン、第三級アミン、及び第四級アンモニウム塩などが挙げられる。(e)成分は、1種を単独で使用してもよいし、2種以上を併用してもよい。
(e)成分としては、耐熱性、難燃性及び金属箔との接着性等の観点からは、イミダゾール類及びその誘導体が好ましく、その中でも、200℃以下での比較的低温での硬化成形性、及びワニス又はプリプレグの経日安定性の観点から、下記一般式(1)で表される、イソシアネート樹脂との反応により得られるイミダゾール誘導体、又は、下記一般式(2)で表される、イミダゾール基がエポキシ樹脂と反応することにより得られるイミダゾール誘導体がより好ましい。
(一般式(1)中、Re1~Re4は、それぞれ独立に、水素原子、炭素数1~5の脂肪族炭化水素基又はフェニル基である。Dは、炭素数1~10のアルキレン基又は炭素数6~12の芳香族炭化水素基である。)
(一般式(2)中、Re5~Re8は、それぞれ独立に、水素原子、炭素数1~5の脂肪族炭化水素基又はフェニル基である。Bは、単結合、炭素数1~10のアルキレン基、炭素数2~5のアルキリデン基、エーテル基又はスルホニル基である。)
前記一般式(1)中のD及び前記一般式(2)中のBが表す炭素数1~10のアルキレン基としては、メチレン基、テトラメチレン基、ヘキサメチレン基、デカメチレン基等が挙げられる。これらの中でも、炭素数1~6のアルキレン基が好ましく、炭素数2~6のアルキレン基がより好ましく、ヘキサメチレン基がさらに好ましい。
Dが表す炭素数6~12の芳香族炭化水素基としては、フェニレン基、ビフェニリレン基、ナフチレン基等が挙げられる。
前記一般式(2)中のBが表す炭素数2~5のアルキリデン基としては、エチリデン基、イソプロピリデン基等が挙げられる。これらの中でも、イソプロピリデン基が好ましい。
一般式(1)中のDとしては、炭素数1~10のアルキレン基が好ましく、より好ましい基は前述の通りである。
一般式(2)中のRe5~Re8としては、水素原子、フェニル基が好ましく、特にRe5及びRe7が水素原子で、且つRe6及びRe8がフェニル基であることが好ましい。
一般式(2)中のBとしては、炭素数2~5のアルキリデン基が好ましく、より好ましい基は前述の通りである。
熱硬化性樹脂組成物が(e)成分を含有する場合、その含有量は、樹脂成分100質量部に対して、0.1~10質量部が好ましく、0.1~5質量部がより好ましく、0.1~2質量部がさらに好ましい。0.1質量部以上とすることにより、優れた耐熱性、難燃性及び金属箔との接着性が得られる傾向があり、また、10質量部以下とすることにより、耐熱性、経日安定性及びプレス成形性が低下し難い傾向がある。
本実施形態の熱硬化性樹脂組成物は、さらに、(f)モノアミン化合物[以下、(f)成分と称することがある。]を含有してなるものであってもよいし、含有していなくてもよい。本実施形態の熱硬化性樹脂組成物は、(f)成分を含有することにより、耐熱性をより向上させることができる。
(f)成分としては、下記一般式(f)で表される化合物が好ましい。
(式中、Rf1は、各々独立に、酸性置換基である、水酸基、カルボキシ基又はスルホン酸基であり、Rf2は、各々独立に、炭素数1~5の脂肪族炭化水素基又はハロゲン原子である。xは1~5の整数、yは0~4の整数である。)
xは1~5の整数であり、高耐熱性、低比誘電率、高ガラス転移温度、低熱膨張性及び成形性の観点から、好ましくは1~3の整数、より好ましくは1又は2、さらに好ましくは1である。
Rf2が示す炭素数1~5のアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、t-ブチル基、n-ペンチル基等が挙げられる。該アルキル基としては、好ましくは炭素数1~3のアルキル基である。
Rf2が示すハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。
yは0~4の整数であり、高耐熱性、低比誘電率、高ガラス転移温度、低熱膨張性及び成形性の観点から、好ましくは0~3の整数、より好ましくは0~2の整数、さらに好ましくは0又は1、特に好ましくは0である。
なお、xが2~5の整数の場合、複数のRf1は同一であってもよいし、異なっていてもよい。また、yが2~4の整数の場合、複数のRf2は同一であってもよいし、異なっていてもよい。
本実施形態の熱硬化性樹脂組成物が(f)成分を含有する場合、その含有量は、耐熱性を維持しつつ、熱膨張率を低減する観点から、熱硬化性樹脂組成物の樹脂成分100質量部に対して、0.2~5質量部が好ましい。
本実施形態の熱硬化性樹脂組成物は、熱硬化性の性質を損なわない程度に、任意に公知の熱可塑性樹脂、有機充填材、難燃剤、難燃助剤、紫外線吸収剤、過酸化物、酸化防止剤、光重合開始剤、蛍光増白剤、接着性向上剤等を含有していてもよい。
難燃剤としては、芳香族リン酸エステル化合物、ホスファゼン化合物、ホスフィン酸エステル、ホスフィン酸化合物の金属塩、赤リン、9,10-ジヒドロ-9-オキサ-10-ホスファフェナントレン-10-オキシド及びその誘導体等のリン系難燃剤;スルファミン酸グアニジン、硫酸メラミン、ポリリン酸メラミン、メラミンシアヌレート等の窒素系難燃剤;臭素、塩素等を含有する含ハロゲン系難燃剤などが挙げられる。
難燃助剤としては、三酸化アンチモン、アンチモン酸ナトリウム、ZnS、ホウ酸亜鉛、スズ酸亜鉛、モリブデン酸亜鉛等の無機系難燃剤などが挙げられる。これらは、必要に応じてタルク等の担体に担持されていてもよい。
なお、難燃剤として機能する物質及び難燃助剤として機能する物質は、たとえ無機化合物であっても無機充填材には分類せず、難燃剤又は難燃助剤として分類する。
過酸化物としては、前記(a)成分と前記(c)成分の反応を促進するものが好ましく、例えば、α,α’-ジ(t-ブチルパーオキシ)ジイソプロピルベンゼン等の有機過酸化物などが挙げられる。本実施形態の熱硬化性樹脂組成物が過酸化物を含有する場合、その含有量は、特に制限されるものではないが、樹脂成分100質量部に対して0.1~3質量部が好ましく、0.3~2質量部がより好ましく、0.5~1.5質量部がさらに好ましい。
酸化防止剤としては、ヒンダードフェノール系酸化防止剤、ヒンダードアミン系酸化防止剤等が挙げられる。
光重合開始剤としては、ベンゾフェノン類、ベンジルケタール類、チオキサントン系等の光重合開始剤が挙げられる。
蛍光増白剤としては、スチルベン誘導体の蛍光増白剤等が挙げられる。
接着性向上剤としては、尿素シラン等の尿素化合物、前記カップリング剤などが挙げられる。
本実施形態の熱硬化性樹脂組成物は、プリプレグ等の製造に用いるために、各成分が有機溶媒中に溶解又は分散されたワニスの状態としてもよい。つまり、ワニスも本実施形態の熱硬化性樹脂組成物に含まれる。
ワニスに用いる有機溶媒としては、メタノール、エタノール、プロパノール、ブタノール、メチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のアルコール系溶媒;アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒;酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート等のエステル系溶媒;テトラヒドロフラン等のエーテル系溶媒;トルエン、キシレン、メシチレン等の芳香族系溶媒;ジメチルホルムアミド、ジメチルアセトアミド、N-メチルピロリドン等の窒素原子含有溶媒;ジメチルスルホキシド等の硫黄原子含有溶媒などが挙げられる。有機溶媒は、1種を単独で使用してもよいし、2種以上を併用してもよい。
これらの中でも、溶解性の観点から、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、メチルセロソルブ、プロピレングリコールモノメチルエーテルが好ましく、低毒性である点から、メチルイソブチルケトン、シクロヘキサノン、プロピレングリコールモノメチルエーテルがより好ましい。
ワニスの固形分濃度は、40~90質量%が好ましく、50~80質量%がより好ましい。ワニスの固形分濃度が前記範囲内であると、塗工性を良好に保ち、適切な樹脂組成物付着量のプリプレグを得ることができる。
本実施形態のプリプレグは、本実施形態の熱硬化性樹脂組成物を含有してなるものであり、より詳細には、Bステージ化した熱硬化性樹脂組成物を含有するものである。
本実施形態のプリプレグは、例えば、本実施形態の熱硬化性樹脂組成物を、繊維基材に含浸し、加熱等によってBステージ化することで製造することができる。ここで、本明細書においてB-ステージ化とは、JIS K6900(1994年)にて定義されるB-ステージの状態にすることであり、半硬化とも称される。
前記繊維基材としては、各種の電気絶縁材料用積層板に用いられている周知のものが使用できる。その材質の例としては、Eガラス、Sガラス、低誘電ガラス、Qガラス等の無機物繊維;低誘電ガラスポリイミド、ポリエステル、テトラフルオロエチレン等の有機繊維;並びにそれらの混合物などが挙げられる。特に、誘電特性が優れる基材を得る観点から、低誘電ガラス、Qガラスが好ましい。
本実施形態のプリプレグは耐デスミア性に優れているため、厚み40~300μmのプリプレグ、さらには厚み40~200μmのプリプレグにしたとしても、デスミア処理の前後の重量変化量が小さく抑えられる点で優れている。該厚みは、加熱乾燥後のプリプレグの厚みである。
本実施形態の積層板は、本実施形態のプリプレグを含有してなる積層板である。
本実施形態の積層板は、本実施形態のプリプレグを積層成形することで得られる。具体的には、本実施形態のプリプレグ1枚を準備するか又はプリプレグを2~20枚重ねたものを準備し、その片面又は両面に銅、アルミニウム等の金属箔を配置した構成で積層成形することにより製造することができる。該製造方法により、本実施形態のプリプレグを用いて形成された絶縁層(該絶縁層はCステージ化されている。)と、その片面又は両面に配置された金属箔と、を有する積層板が得られる。金属箔は、電気絶縁材料用途で用いるものであれば特に制限されない。なお、本実施形態の積層板の片面又は両面に金属箔が配置された積層板を、特に、金属張り積層板と称する。また、本明細書においてC-ステージ化とは、JIS K6900(1994年)にて定義されるC-ステージの状態にすることである。
積層板及び金属張り積層板を製造する際の成形条件は、例えば、電気絶縁材料用積層板及び多層板の手法が適用でき、多段プレス、多段真空プレス、連続成形、オートクレーブ成形機等を使用し、温度100~250℃、圧力0.2~10MPa、加熱時間0.1~5時間で成形することができる。また、本実施形態のプリプレグと内層用配線板とを組合せ、積層成形することによって、積層板を製造することもできる。
本実施形態のプリント配線板は、本実施形態の積層板又は金属張り積層板に回路形成して得られるプリント配線板である。
回路形成方法としては、サブトラクティブ法、フルアディティブ法、セミアディティブ法(SAP:Semi Additive Process)、モディファイドセミアディティブ法(m-SAP:modified Semi Additive Process)等の公知の方法が挙げられる。
また、例えば、回路形成した積層板を、本実施形態のプリプレグを間に挟んだ状態で複数積層した後、加熱プレス加工することによって多層化することもできる。その後、ドリル加工又はレーザ加工によるスルーホール又はブラインドビアホールの形成と、めっき又は導電性ペーストによる層間配線の形成を経ることによって、多層プリント配線板を製造することができる。
本開示は、本実施形態のプリント配線板及び半導体素子を含有する半導体パッケージも提供する。半導体パッケージは、前記多層プリント配線板の所定の位置に半導体チップ、メモリ等の半導体素子を搭載し、封止樹脂等によって半導体素子を封止することによって製造できる。
なお、各例で得られた銅張積層板は、以下の方法で性能を測定及び評価した。
各例で製造した銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除き、裁断することで5mm(X方向)×5mm角(Y方向)の評価基板を作製した。なお、前記裁断は、裁断面がガラス繊維方向に沿う状態で実施した。
該評価基板を用いて、TMA試験装置(ティー・エイ・インスツルメント・ジャパン(株)製、TMAQ400EM)によって、圧縮法で熱機械分析を行った。熱膨張率の測定方向はX方向とした。評価基板を前記装置に装着後、昇温速度10℃/分で260℃まで昇温し、降温速度10℃/分で10℃まで降温した後、再度、昇温速度10℃/分で320℃まで昇温した。2回目の測定における50℃から120℃までの平均熱膨張率を算出し、これを熱膨張率の値とした。
各例で製造した銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除き、裁断することで25mm×40mm角の評価基板を作製した。なお、前記裁断は、裁断面がガラス繊維方向に沿う状態で実施した。
該評価基板を用いて、曲げ弾性率試験装置((株)オリエンテック製、5トンテンシロン)によって、25℃、クロスヘッド速度1mm/min、スパン間距離20mmの条件で測定した。曲げ弾性率の測定方向は板厚方向とした。
銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いた40mm×40mmの評価基板を、膨潤液である「スエリングディップ・セキュリガントP」(グリコールエーテル類、水酸化ナトリウムの水溶液、アトテックジャパン(株)製)に70℃で5分間浸漬した。次に、粗化液である「コンセントレート・コンパクトP」(KMnO4:60g/L、NaOH:40g/Lの水溶液、アトテックジャパン(株)製)に80℃で15分間浸漬した。最後に、中和液である「リダクションショリューシン・セキュリガントP」(硫酸の水溶液、アトテックジャパン(株)製)に4℃で5分間浸漬した。その後、80℃で10分間乾燥した。以上の様に実施することで、デスミア処理を行った。
デスミア処理前の乾燥重量に対するデスミア処理後の重量減少量(g/m2)を算出し、これを耐デスミア性の指標とした。デスミア処理後の重量減少量が小さい程、耐デスミア性に優れる。
なお、実施例4においてデスミア処理した後の基板表面のSEM写真を図2に示す。
(1.アゾメチン変性シロキサン[(a2’)成分]の合成)
温度計、攪拌装置、及び還流冷却管付き水分定量器を備えた容積2Lの反応容器に、両末端アミノ変性シリコーン「XF42-C5379」(商品名、モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製、官能基当量:740g/eq)592質量部、テレフタルアルデヒド33質量部及びプロピレングリコールモノメチルエーテル939質量部を入れ、115℃で2時間反応させた後、125℃まで昇温することで常圧濃縮により脱水し、アゾメチン変性シロキサン含有溶液を得た。
(2.(a)成分である変性マレイミド樹脂(A)の合成)
温度計、攪拌装置、及び還流冷却管付き水分定量器を備えた内容積2Lの反応容器に、前記アゾメチン変性シロキサン含有溶液119質量部(固形分換算量)((a2’)成分)、2,2-ビス[4-(4-マレイミドフェノキシ)フェニル]プロパン((a1)成分)161質量部、プロピレングリコールモノメチルエーテル376質量部を入れ、120℃で4時間反応させて変性マレイミド樹脂[以下、変性マレイミド樹脂(A-1)と称する。]含有溶液を得た。
希釈溶剤としてメチルエチルケトンを使用し、表1又は表2に記載された各成分及び各配合量で混合してから6時間攪拌し、樹脂成分65質量%のワニスを調製した。
次に、得られたワニスを厚さ0.1mmのEガラスクロスに含浸塗工し、110℃で3分加熱乾燥することにより、樹脂含有量49~51質量%のプリプレグ(厚み:約100μm)を得た。
このプリプレグを4枚重ね、12μmの電解銅箔を上下に配置し、圧力3.0MPa、昇温速度4.0℃/分で240℃まで昇温した後、85分間保持することによって、4枚重ねの前記プリプレグをCステージ化し、放圧後、30分間冷却することによって銅張積層板を得た。得られた銅張積層板を用いて、前記測定及び評価を行った。結果を表1及び表2に示す。
[(a)少なくとも1個のN-置換マレイミド基を有するマレイミド化合物]
a-1:合成例1で合成した変性マレイミド樹脂(A-1)
a-2:ポリフェニルメタンマレイミド、(a1)成分、融点70~145℃、下記化学構造式参照
(n1は1~10の整数である。)
b-1:溶融球状シリカ(小)(平均粒子径:50nm、頻度分布におけるピークの極大は粒子径30nmに存在する。)
b-2:溶融球状シリカ(中)(平均粒子径:0.3~0.8μm、頻度分布におけるピークの極大は粒子径0.6μmに存在する。)
b-3:溶融球状シリカ(大)(商品名:SO-C4、アドマテックス(株)製、平均粒子径:0.9~1.2μm、頻度分布におけるピークの極大は粒子径1.0μmに存在する。)700gを、KBM-903(商品名、信越化学工業(株)製、3-アミノプロピルトリメトキシシラン)7gを加えたメチルイソブチルケトン溶液300gに攪拌しながら加え、溶融球状シリカのメチルイソブチル溶液を作製し、これをb-3成分として使用した。
なお、上記平均粒子径は、粒子の全体積を100%として粒子径による累積度数分布曲線を求めたとき、体積50%に相当する点の粒子径(体積平均粒子径)のことであり、レーザ回折散乱法を用いた粒度分布測定装置「UPA-UT151」(マイクロトラック・ベル(株)製)で測定した値である。
また、上記の頻度分布における極大が存在する位置は、粒子の全体積を100%として粒子径による頻度分布曲線において、山になっているピークにおいて頻度が極大値となる位置とした。当該測定は、レーザ回折散乱法を用いた粒度分布測定装置「UPA-UT151」(マイクロトラック・ベル(株)製)で行なった。
c-1:「SBA01A」、商品名、アリル化ビフェニレン樹脂、群栄化学工業(株)製、(c1)成分、下記化学構造式参照
c-2:「LVA01」、商品名、アリル化フェノール樹脂、群栄化学工業(株)製、(c1)成分、下記化学構造式参照
c-3:「PPN-80」、商品名、プロペニル化フェノール樹脂、群栄化学工業(株)製、(c1)成分、下記化学構造式参照
c-4:「BPN01」、商品名、プロペニル化ビフェニレン樹脂、群栄化学工業(株)製、(c1)成分、下記化学構造式参照
(上記SBA01A中のRc1は、それぞれ独立に、有機基である。nc1~nc3はいずれも鍵括弧で囲まれた部位の繰り返し単位数を表し、それぞれ独立に3~30の整数である。)
c-6:「TAIC」、商品名、四国化成工業(株)製、(c2)成分、下記化学構造式参照
c-7:「DD-1」、商品名、四国化成工業(株)製、(c2)成分、下記化学構造式参照
(式中、Rc2は、エーテル基及びヒドロキシル基からなる群から選択される少なくとも1種を含んでいてもよい炭素数2~18の脂肪族炭化水素基である。)
d-1:ナフタレン型エポキシ樹脂
一方、無機充填材の含有量が53体積%未満の熱硬化性樹脂組成物を用いた比較例1では、やはり熱膨張率を低減し切れていない結果となった。そこで、無機充填材の含有量を53体積%以上に調整した比較例2では低熱膨張性を向上させることができたが、耐デスミア性が不十分であった。比較例の結果から、低熱膨張性と高い耐デスミア性を共に満足させることは容易ではなく、且つ、それに加えて高弾性とすることも容易ではないことが分かる。
Claims (14)
- (a)少なくとも1個のN-置換マレイミド基を有するマレイミド化合物及び(b)無機充填材を含有してなり、且つ、前記(b)無機充填材の含有量が熱硬化性樹脂組成物総量に対して53~65体積%である熱硬化性樹脂組成物であって、
さらに、(c)少なくとも2個の不飽和脂肪族炭化水素基を有する化合物を含有してなる、熱硬化性樹脂組成物。 - 前記(a)成分が、(a1)少なくとも2個のN-置換マレイミド基を有するマレイミド化合物と(a2)少なくとも2個の1級アミノ基を有するシリコーン化合物との反応物を含有する、請求項1に記載の熱硬化性樹脂組成物。
- 前記(b)成分の体積基準の粒子径分布のピークの極大が、少なくとも、0.01μm以上0.1μm未満の範囲に存在する、請求項1又は2に記載の熱硬化性樹脂組成物。
- 前記(b)成分の体積基準の粒子径分布のピークの極大が、0.01μm以上0.1μm未満の範囲と0.1μm以上10μm以下の範囲の両方に存在する、請求項1~3のいずれか1項に記載の熱硬化性樹脂組成物。
- 前記(c)成分が、少なくとも3個の不飽和脂肪族炭化水素基を有する化合物である、請求項1~4のいずれか1項に記載の熱硬化性樹脂組成物。
- 前記(c)成分が、(c1)少なくとも2個の不飽和脂肪族炭化水素基を有し、且つ、芳香族炭化水素基を有する化合物である、請求項1~4のいずれか1項に記載の熱硬化性樹脂組成物。
- 前記(c)成分が有する不飽和脂肪族炭化水素基が、ビニル基、イソプロペニル基、1-プロペニル基、アリル基、1-メチルアリル基及び3-ブテニル基からなる群から選択される少なくとも1種である、請求項1~7のいずれか1項に記載の熱硬化性樹脂組成物。
- 請求項1~8のいずれか1項に記載の熱硬化性樹脂組成物を含有してなるプリプレグ。
- 厚みが40~300μmである、請求項9に記載のプリプレグ。
- 請求項9又は10に記載のプリプレグを含有してなる積層板。
- 請求項11に記載の積層板の片面又は両面に金属箔が配置された金属張り積層板。
- 請求項11に記載の積層板又は請求項12に記載の金属張り積層板に回路形成して得られる、プリント配線板。
- 請求項13に記載のプリント配線板及び半導体素子を含有する半導体パッケージ。
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