JP6545924B2 - Roughened hardened body, laminate, printed wiring board and semiconductor device - Google Patents
Roughened hardened body, laminate, printed wiring board and semiconductor device Download PDFInfo
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- JP6545924B2 JP6545924B2 JP2012284846A JP2012284846A JP6545924B2 JP 6545924 B2 JP6545924 B2 JP 6545924B2 JP 2012284846 A JP2012284846 A JP 2012284846A JP 2012284846 A JP2012284846 A JP 2012284846A JP 6545924 B2 JP6545924 B2 JP 6545924B2
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- CUQCMXFWIMOWRP-UHFFFAOYSA-N phenyl biguanide Chemical compound NC(N)=NC(N)=NC1=CC=CC=C1 CUQCMXFWIMOWRP-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- LYKRPDCJKSXAHS-UHFFFAOYSA-N phenyl-(2,3,4,5-tetrahydroxyphenyl)methanone Chemical compound OC1=C(O)C(O)=CC(C(=O)C=2C=CC=CC=2)=C1O LYKRPDCJKSXAHS-UHFFFAOYSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 239000002356 single layer Substances 0.000 description 1
- 101150114085 soc-2 gene Proteins 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical class SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Classifications
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- B32B15/092—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 comprising epoxy resins
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Description
本発明は、粗化硬化体、積層体、プリント配線板及び半導体装置に関する。 The present invention relates to a roughened cured product, a laminate, a printed wiring board and a semiconductor device.
プリント配線板の製造技術として、絶縁層と導体層を交互に積み重ねるビルドアップ方式による製造方法が知られている。ビルドアップ方式による製造方法において、一般に、絶縁層は樹脂組成物を熱硬化させて形成される。例えば、特許文献1には、シリカ粒子を含有する樹脂組成物を熱硬化させて得た硬化体を粗化処理して絶縁層を形成する技術が開示されている。 As a manufacturing technique of a printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the build-up type manufacturing method, the insulating layer is generally formed by thermally curing the resin composition. For example, Patent Document 1 discloses a technique for roughening a cured product obtained by thermally curing a resin composition containing silica particles to form an insulating layer.
配線密度の更なる向上が求められる中で、プリント配線板のビルドアップによる積層数は増加する傾向にあるが、積層数の増加に伴って絶縁層と導体層との熱膨張の差によるクラックや回路歪みの発生が問題となる。斯かるクラックや回路歪みの問題を抑制する技術として、例えば、特許文献2には、樹脂組成物におけるシリカ粒子等の無機充填材の含有量を高めることによって、形成される絶縁層の熱膨張率を低く抑える技術が開示されている。 While there is a demand for further improvement in wiring density, the number of laminations tends to increase due to the buildup of the printed wiring board. However, with the increase in the number of laminations, cracks due to the difference in thermal expansion between the insulating layer and the conductor layer The occurrence of circuit distortion is a problem. As a technique for suppressing such problems of cracks and circuit distortion, for example, Patent Document 2 describes the thermal expansion coefficient of an insulating layer formed by increasing the content of an inorganic filler such as silica particles in a resin composition. A technique for keeping the
特許文献1記載の技術では、粗化処理において硬化体表面のシリカ粒子が脱離することによって、導体層に対して十分な剥離強度を呈する絶縁層が実現される。しかしながら、熱膨張率の低い絶縁層を形成すべく、シリカ粒子等の無機充填材の含有量の高い樹脂組成物を用いると、粗化処理後の硬化体の表面が高粗度になってしまう上に、導体層に対する剥離強度も低下してしまう場合のあることを本発明者らは見出した。 In the technique described in Patent Document 1, an insulating layer exhibiting sufficient peel strength with respect to the conductor layer is realized by the detachment of the silica particles on the surface of the cured body in the roughening treatment. However, if a resin composition having a high content of inorganic filler such as silica particles is used to form an insulating layer having a low coefficient of thermal expansion, the surface of the hardened body after the roughening treatment will have a high degree of roughness. The present inventors have found that the peel strength to the conductor layer may also be reduced.
本発明は、無機充填材の含有量が高いという特性は保持しつつ、表面の粗度が低く且つ導体層に対して優れた剥離強度を呈する粗化硬化体を提供することを課題とする。 An object of the present invention is to provide a roughened cured product which has low surface roughness and exhibits excellent peel strength to a conductor layer while maintaining the property that the content of the inorganic filler is high.
本発明者らは、上記の課題につき鋭意検討した結果、粗化硬化体の表面におけるケイ素原子(Si)と酸素原子(O)の量を特定範囲とすることにより上記課題を解決できることを見出し、本発明を完成するに至った。 The inventors of the present invention have found that the above-mentioned problems can be solved by setting the amounts of silicon atoms (Si) and oxygen atoms (O) on the surface of the roughened hardened body to a specific range as a result of earnestly examining the above problems. The present invention has been completed.
すなわち、本発明は以下の内容を含む。
[1] 無機充填材含有量が50質量%以上である熱硬化性樹脂組成物の熱硬化体を粗化処理して得られる粗化硬化体であって、
X線光電子分光法により測定した、表面のSi量が25atom%以下であり、かつ表面のO量が25atom%以上である、粗化硬化体。
[2] 表面のSi量に対するO量の比(O/Si)が2.1以上である、[1]に記載の粗化硬化体。
[3] 熱硬化体の表面の引っかき硬度(JIS K5600−5−4)がH以上である、[1]又は[2]に記載の粗化硬化体。
[4] X線光電子分光法により測定した、熱硬化体の表面のSi量が2atom%未満である、[1]〜[3]のいずれかに記載の粗化硬化体。
[5] 粗化処理における単位表面積当たりのエッチング量が2g/m2以下である、[1]〜[4]のいずれかに記載の粗化硬化体。
[6] 表面の算術平均粗さRaが300nm以下である、[1]〜[5]のいずれかに記載の粗化硬化体。
[7] [1]〜[6]のいずれかに記載の粗化硬化体と、該粗化硬化体の表面に形成された導体層とを備える積層体。
[8] 粗化硬化体と導体層との剥離強度が0.3kgf/cm以上である、[7]に記載の積層体。
[9] [1]〜[6]のいずれかに記載の粗化硬化体により絶縁層が形成されたプリント配線板。
[10] [9]に記載のプリント配線板を含む半導体装置。
That is, the present invention includes the following contents.
[1] A roughened cured body obtained by roughening a thermosetting body of a thermosetting resin composition having an inorganic filler content of 50% by mass or more,
A roughened cured product having a surface Si content of 25 atom% or less and a surface O content of 25 atom% or more as measured by X-ray photoelectron spectroscopy.
[2] The roughened cured product according to [1], wherein the ratio of the amount of O to the amount of Si on the surface (O / Si) is 2.1 or more.
[3] The roughened cured product according to [1] or [2], wherein the scratch hardness (JIS K5600-5-4) of the surface of the thermally cured product is H or more.
[4] The roughened cured product according to any one of [1] to [3], wherein the amount of Si on the surface of the thermally cured product is less than 2 atom% as measured by X-ray photoelectron spectroscopy.
[5] The roughened cured product according to any one of [1] to [4], wherein the etching amount per unit surface area in the roughening treatment is 2 g / m 2 or less.
[6] The roughened cured product according to any one of [1] to [5], wherein the arithmetic mean roughness Ra of the surface is 300 nm or less.
[7] A laminate comprising the roughened cured product according to any one of [1] to [6], and a conductor layer formed on the surface of the roughened cured product.
[8] The laminate according to [7], wherein the peeling strength between the roughened cured product and the conductor layer is 0.3 kgf / cm or more.
[9] A printed wiring board in which an insulating layer is formed of the roughened cured product according to any one of [1] to [6].
[10] A semiconductor device including the printed wiring board according to [9].
本発明によれば、無機充填材の含有量が高いという特性は保持しつつ、表面の粗度が低く且つ導体層に対して優れた剥離強度を呈する粗化硬化体を提供することができる。 According to the present invention, it is possible to provide a roughened cured product having a low surface roughness and exhibiting excellent peel strength to a conductor layer while maintaining the property that the content of the inorganic filler is high.
以下、本発明をその好適な実施形態に即して詳細に説明する。 Hereinafter, the present invention will be described in detail in line with its preferred embodiments.
[粗化硬化体]
本発明の粗化硬化体は、無機充填材含有量が50質量%以上である熱硬化性樹脂組成物の熱硬化体を粗化処理して得られたものであり、X線光電子分光法により測定した、表面のSi量が25atom%以下であり、かつ表面のO量が25atom%以上であることを特徴とする。
[Roughened hardened body]
The roughened cured product of the present invention is obtained by roughening a thermosetting product of a thermosetting resin composition having an inorganic filler content of 50% by mass or more, and is determined by X-ray photoelectron spectroscopy. The measured amount of Si on the surface is 25 atom% or less, and the amount of O on the surface is 25 atom% or more.
表面が低粗度であっても導体層に対して優れた剥離強度を呈する粗化硬化体を得る観点から、X線光電子分光法により測定した、本発明の粗化硬化体の表面のSi量は、好ましくは24atom%以下、より好ましくは22atom%以下、さらに好ましくは20atom%以下、さらにより好ましくは18atom%以下、特に好ましくは16atom%以下、14atom%以下、12atom%以下、10atom%以下、又は8atom%以下である。斯かるSi量の下限は特に制限されず、通常、0atom%以上であり、好ましくは0.01atom%以上、より好ましくは0.5atom%以上、更に好ましくは1atom%以上である。
なお、粗化硬化体の表面のSi原子は、後述する無機充填材及びその表面処理剤に由来するものである。Si原子は、導体層(金属層)との密着性に寄与しない非極性原子であることから、導体層に対して優れた剥離強度を呈する粗化硬化体を得る観点からは、本発明の粗化硬化体の表面のSi量は少ないほど好ましい。
The amount of Si on the surface of the roughened cured product of the present invention measured by X-ray photoelectron spectroscopy from the viewpoint of obtaining a roughened cured product exhibiting excellent peel strength to the conductor layer even if the surface has a low roughness Is preferably 24 atom% or less, more preferably 22 atom% or less, still more preferably 20 atom% or less, still more preferably 18 atom% or less, particularly preferably 16 atom% or less, 14 atom% or less, 12 atom% or less, 10 atom% or less It is 8 atom% or less. The lower limit of the amount of Si is not particularly limited, and is usually 0 atom% or more, preferably 0.01 atom% or more, more preferably 0.5 atom% or more, and still more preferably 1 atom% or more.
In addition, the Si atom of the surface of a roughening hardening body originates in the inorganic filler mentioned later and its surface treating agent. Since Si atoms are nonpolar atoms that do not contribute to adhesion with the conductor layer (metal layer), the rough of the present invention is obtained from the viewpoint of obtaining a roughened cured product exhibiting excellent peel strength to the conductor layer. It is preferable that the amount of Si on the surface of the chemical-hardened body be as small as possible.
また、X線光電子分光法により測定した、本発明の粗化硬化体の表面のO量は、好ましくは26atom%以上、より好ましくは27atom%以上、さらに好ましくは28atom%以上、さらにより好ましくは29atom%以上、特に好ましくは30atom%以上である。斯かるO量の上限は、通常、65atom%以下であり、好ましくは60atom%以下、より好ましくは55atom%以下、さらに好ましくは50atom%以下、さらにより好ましくは45atom%以下、特に好ましくは40atom%以下、38atom%以下、36atom%以下、34atom%以下、又は32atom%以下である。
なお、粗化硬化体の表面のO原子は、後述する無機充填材、その表面処理剤、熱硬化性樹脂、硬化剤等のO原子含有成分に由来するものである。O原子は、導体層(金属層)との密着性に寄与する極性原子であることから、導体層に対して優れた剥離強度を呈する粗化硬化体を得る観点から、本発明の粗化硬化体の表面のO量は上記の下限値の条件を満たすことが好ましい。
The amount of O on the surface of the roughened cured product of the present invention measured by X-ray photoelectron spectroscopy is preferably 26 atom% or more, more preferably 27 atom% or more, still more preferably 28 atom% or more, even more preferably 29 atom % Or more, particularly preferably 30 atom% or more. The upper limit of the amount of O is usually 65 atom% or less, preferably 60 atom% or less, more preferably 55 atom% or less, still more preferably 50 atom% or less, still more preferably 45 atom% or less, particularly preferably 40 atom% or less 38 atom% or less, 36 atom% or less, 34 atom% or less, or 32 atom% or less.
In addition, O atom of the surface of a roughening hardening body originates in O atom containing components, such as an inorganic filler mentioned later, its surface treating agent, thermosetting resin, and a hardening agent. Since the O atom is a polar atom that contributes to the adhesion with the conductor layer (metal layer), the roughening curing of the present invention is performed from the viewpoint of obtaining a roughened cured body exhibiting excellent peel strength to the conductor layer. The amount of O on the surface of the body preferably satisfies the above lower limit condition.
X線光電子分光法による粗化硬化体の表面組成分析は、例えば、下記の測定装置を用いて下記の測定条件により実施することができる。 The surface composition analysis of the roughened cured product by X-ray photoelectron spectroscopy can be performed, for example, under the following measurement conditions using the following measurement apparatus.
〔測定装置〕
装置型式:QUANTERA SXM(アルバックファイ社製 全自動走査型X線光電子分光分析装置)
到達真空度:7.0×10−10Torr
X線源:単色化 Al Kα(1486.6eV)
分光器:静電同心半球型分析器
検出器:多チャンネル式(32 Multi−Channel Detector)
中和銃設定 電子:1.0 V (20μA)、イオン:10.0V(7mA)
〔measuring device〕
Device type: QUANTERA SXM (Full-vacuated full automatic scanning X-ray photoelectron spectrometer)
Ultimate vacuum: 7.0 × 10 -10 Torr
X-ray source: monochromized Al K α (1486.6 eV)
Spectrometer: electrostatic concentric hemispherical analyzer detector: multi-channel (32 Multi-Channel Detector)
Neutralization gun setting Electron: 1.0 V (20 μA), ion: 10.0 V (7 mA)
〔測定条件〕
[サーベイスペクトル(ワイドスキャン)]
X線ビーム径:100μmΦ(HPモード、100.6W、20kV)
測定領域:1400μm×100μm
信号の取り込み角:45.0°
パスエネルギー:280.0eV
〔Measurement condition〕
[Survey spectrum (wide scan)]
X-ray beam diameter: 100 μm HP (HP mode, 100.6 W, 20 kV)
Measurement area: 1400 μm × 100 μm
Signal capture angle: 45.0 °
Path energy: 280.0 eV
表面が低粗度であっても導体層に対して優れた剥離強度を呈する粗化硬化体を得る観点から、粗化硬化体の表面におけるSi量に対するO量の比(O/Si)が2.1以上であることが好ましく、2.2以上であることがより好ましく、2.4以上であることがさらに好ましく、2.6以上であることがさらにより好ましく、2.8以上、3.0以上、3.2以上、3.4以上、3.6以上、又は3.7以上であることが特に好ましい。 The ratio (O / Si) of the amount of O to the amount of Si on the surface of the roughened hardened body is 2 from the viewpoint of obtaining a roughened hardened body that exhibits excellent peel strength to the conductor layer even if the surface has low roughness. 1 or more is preferable, 2.2 or more is more preferable, 2.4 or more is further preferable, and 2.6 or more is further preferable, 2.8 or more, and 3. Particularly preferably, it is 0 or more, 3.2 or more, 3.4 or more, 3.6 or more, or 3.7 or more.
表面のSi原子とO原子の割合を上記範囲とすることにより、本発明の粗化硬化体は、表面が低粗度であっても導体層に対して優れた剥離強度を呈することができる。一実施形態において、本発明の粗化硬化体の表面の算術平均粗さRaは、微細配線形成能向上の観点から、好ましくは350nm未満、より好ましくは300nm以下、さらに好ましくは250nm以下、さらにより好ましくは200nm以下、特に好ましくは180nm以下、160nm以下、140nm以下、120nm以下、100nm以下、又は80nm以下である。算術平均粗さRaの下限値は特に限定されず、20nm、40nmなどとなる。本発明の粗化硬化体と導体層との剥離強度に関しては後述する。
なお、粗化硬化体の表面の算術平均粗さRaは、非接触型表面粗さ計を用いて測定することができる。非接触型表面粗さ計の具体例としては、ビーコインスツルメンツ製の「WYKO NT3300」が挙げられる。
By setting the ratio of Si atoms and O atoms in the surface to the above range, the roughened cured product of the present invention can exhibit excellent peel strength to the conductor layer even if the surface has low roughness. In one embodiment, the arithmetic mean roughness Ra of the surface of the roughened cured product of the present invention is preferably less than 350 nm, more preferably 300 nm or less, still more preferably 250 nm or less, from the viewpoint of improving fine wiring formation ability. It is preferably 200 nm or less, particularly preferably 180 nm or less, 160 nm or less, 140 nm or less, 120 nm or less, 100 nm or less, or 80 nm or less. The lower limit value of the arithmetic average roughness Ra is not particularly limited, and is 20 nm, 40 nm, or the like. The peel strength between the roughened cured product of the present invention and the conductor layer will be described later.
In addition, arithmetic mean roughness Ra of the surface of a roughening hardening body can be measured using a non-contact-type surface roughness meter. A specific example of the noncontact surface roughness tester is "WYKO NT3300" manufactured by Becoin Instruments.
本発明の粗化硬化体は、無機充填材含有量が50質量%以上である熱硬化性樹脂組成物の熱硬化体を粗化処理して得られる。 The roughening cured body of the present invention is obtained by roughening a thermosetting body of a thermosetting resin composition having an inorganic filler content of 50% by mass or more.
表面のSi原子とO原子の割合が所望の範囲にある粗化硬化体を得る観点から、本発明の粗化硬化体を形成するために使用する熱硬化体は、JIS K5600−5−4(ISO 15184)に準拠して測定された、表面の引っかき硬度がH以上であることが好ましく、2H以上であることがより好ましく、3H以上であることがさらに好ましく、4H以上であることが特に好ましい。斯かる引っかき硬度の上限は、8Hであり、好ましくは5H以下である。 From the viewpoint of obtaining a roughened cured product in which the ratio of Si atoms to O atoms on the surface is in a desired range, the thermally cured product used to form the roughened cured product of the present invention is JIS K5600-5-4 ( The scratch hardness of the surface measured according to ISO 15184) is preferably H or more, more preferably 2H or more, still more preferably 3H or more, particularly preferably 4H or more . The upper limit of such scratch hardness is 8H, preferably 5H or less.
熱硬化体はまた、X線光電子分光法により測定した、表面のSi量が、2atom%未満であることが好ましく、1.5atom%以下であることがより好ましく、1.0atom%以下であることがさらに好ましく、0.8atom%以下、0.6atom%以下、0.4atom%以下、又は0.2atom%以下であることが特に好ましい。斯かるSi量の下限は特に制限されず、0atom%であってもよい。 The thermally cured product also preferably has a surface Si content of less than 2 atom%, more preferably 1.5 atom% or less, and 1.0 atom% or less, as measured by X-ray photoelectron spectroscopy. Is more preferably 0.8 atom% or less, 0.6 atom% or less, 0.4 atom% or less, or 0.2 atom% or less. The lower limit of the amount of Si is not particularly limited, and may be 0 atom%.
熱硬化体を粗化処理して粗化硬化体を得るに際して、粗化処理における熱硬化体単位表面積当たりのエッチング量は、表面のSi原子とO原子の割合が所望の範囲にある粗化硬化体を得る観点から、2g/m2以下であることが好ましく、1.8g/m2以下であることがより好ましく、1.6g/m2以下であることがさらに好ましく、1.4g/m2以下であることが特に好ましい。斯かるエッチング量の下限は特に制限されないが、好ましくは0.01g/m2以上であり、より好ましくは0.5g/m2以上である。 When roughening the thermosetting body to obtain a roughening cured body, the etching amount per unit surface area of the thermosetting body in the roughening treatment is a roughening hardening in which the ratio of Si atoms to O atoms on the surface is within a desired range from the viewpoint of obtaining a body, preferably at 2 g / m 2 or less, more preferably more preferably 1.8 g / m 2 or less, 1.6 g / m 2 or less, 1.4 g / m It is particularly preferable that it is 2 or less. The lower limit of the etching amount is not particularly limited, but is preferably 0.01 g / m 2 or more, more preferably 0.5 g / m 2 or more.
本発明の粗化硬化体の厚さは、絶縁性向上の観点から、好ましくは3μm以上、より好ましくは5μm以上、さらに好ましくは10μm以上、さらにより好ましくは15μm以上、特に好ましくは20μm以上である。また本発明の粗化硬化体の厚さは、薄膜化の観点から、好ましくは100μm以下、より好ましくは90μm以下、さらに好ましくは80μm以下、さらにより好ましくは70μm以下、特に好ましくは60μm以下である。 The thickness of the roughened cured product of the present invention is preferably 3 μm or more, more preferably 5 μm or more, still more preferably 10 μm or more, still more preferably 15 μm or more, particularly preferably 20 μm or more from the viewpoint of improving insulation. . The thickness of the roughened cured product of the present invention is preferably 100 μm or less, more preferably 90 μm or less, still more preferably 80 μm or less, still more preferably 70 μm or less, particularly preferably 60 μm or less from the viewpoint of thinning. .
本発明の粗化硬化体は、二層以上からなる複層構造であってもよい。複層構造の粗化硬化体の場合、全体の厚さが上記範囲にあることが好ましい。 The roughened cured product of the present invention may have a multilayer structure comprising two or more layers. In the case of a roughened cured product having a multilayer structure, the overall thickness is preferably in the above range.
以下、本発明の粗化硬化体を形成するために使用する熱硬化性樹脂組成物について説明する。 Hereinafter, the thermosetting resin composition used in order to form the roughening cured body of this invention is demonstrated.
<熱硬化性樹脂組成物>
本発明の粗化硬化体は、無機充填材含有量が50質量%以上である熱硬化性樹脂組成物の熱硬化体を粗化処理して得られる。得られる粗化硬化体(絶縁層)の熱膨張率を十分に低下させる観点から、熱硬化性樹脂組成物中の無機充填材の含有量は、好ましくは55質量%以上であり、より好ましくは60質量%以上、さらに好ましくは65質量%以上である。
なお、本発明において、熱硬化性樹脂組成物を構成する各成分の含有量は、熱硬化性樹脂組成物中の不揮発成分の合計を100質量%としたときの値である。
<Thermosetting resin composition>
The roughening cured body of the present invention is obtained by roughening a thermosetting body of a thermosetting resin composition having an inorganic filler content of 50% by mass or more. The content of the inorganic filler in the thermosetting resin composition is preferably 55% by mass or more, and more preferably, from the viewpoint of sufficiently reducing the coefficient of thermal expansion of the roughened cured product (insulating layer) to be obtained. 60 mass% or more, more preferably 65 mass% or more.
In addition, in this invention, content of each component which comprises a thermosetting resin composition is a value when the sum total of the non volatile component in a thermosetting resin composition is 100 mass%.
表面のSi原子とO原子の割合が特定範囲にある本発明の粗化硬化体においては、導体層に対する剥離強度を低下させることなく、無機充填材の含有量を更に高めることができる。例えば、熱硬化性樹脂組成物中の無機充填材の含有量は、66質量%以上、68質量%以上、70質量%以上、72質量%以上、74質量%以上、76質量%以上、又は78質量%以上にまで高めてよい。 In the roughened cured product of the present invention in which the ratio of Si atoms to O atoms on the surface is in a specific range, the content of the inorganic filler can be further increased without decreasing the peel strength to the conductor layer. For example, the content of the inorganic filler in the thermosetting resin composition is 66 mass% or more, 68 mass% or more, 70 mass% or more, 72 mass% or more, 74 mass% or more, 76 mass% or more, or 78 You may raise to more than mass%.
熱硬化性樹脂組成物中の無機充填材の含有量の上限は、該熱硬化性樹脂組成物の熱硬化体の機械強度低下防止の観点から、好ましくは95質量%以下、より好ましくは90質量%以下、更に好ましくは85質量%以下である。 The upper limit of the content of the inorganic filler in the thermosetting resin composition is preferably 95% by mass or less, more preferably 90 mass%, from the viewpoint of preventing the reduction in mechanical strength of the thermosetting body of the thermosetting resin composition. % Or less, more preferably 85% by mass or less.
無機充填材としては、例えば、シリカ、窒化ケイ素、アルミナ、硫酸バリウム、タルク、クレー、雲母粉、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、酸化マグネシウム、窒化ホウ素、ホウ酸アルミニウム、チタン酸バリウム、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸マグネシウム、チタン酸ビスマス、酸化チタン、ジルコン酸バリウム、及びジルコン酸カルシウム等が挙げられる。これらの中でも無定形シリカ、溶融シリカ、結晶シリカ、合成シリカ、中空シリカ等のシリカが特に好適である。またシリカとしては球状シリカが好ましい。無機充填材は1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。市販されている球状溶融シリカとして、(株)アドマテックス製「SOC2」、「SOC1」が挙げられる。 As the inorganic filler, for example, silica, silicon nitride, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, titanium And barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate and the like. Among these, silica such as amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like are particularly preferable. Moreover, as silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more. Examples of commercially available spherical fused silica include "SOC2" and "SOC1" manufactured by Admatechs Co., Ltd.
無機充填材の平均粒径は0.01μm〜2μmの範囲が好ましく、0.05μm〜1.5μmの範囲がより好ましく、0.07μm〜1μmの範囲が更に好ましく、0.1μm〜0.8μmが更により好ましい。無機充填材の平均粒径はミー(Mie)散乱理論に基づくレーザー回折・散乱法により測定することができる。具体的にはレーザー回折散乱式粒度分布測定装置により、無機充填材の粒度分布を体積基準で作成し、そのメディアン径を平均粒径とすることで測定することができる。測定サンプルは、無機充填材を超音波により水中に分散させたものを好ましく使用することができる。レーザー回折散乱式粒度分布測定装置としては、株式会社堀場製作所製LA−500等を使用することができる。 The average particle diameter of the inorganic filler is preferably in the range of 0.01 μm to 2 μm, more preferably in the range of 0.05 μm to 1.5 μm, still more preferably in the range of 0.07 μm to 1 μm, 0.1 μm to 0.8 μm Even more preferred. The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering type particle size distribution measuring device, and the median diameter can be measured as an average particle size. As a measurement sample, one in which an inorganic filler is dispersed in water by ultrasonic waves can be preferably used. As laser diffraction scattering type particle size distribution measuring apparatus, LA-500 etc. by Horiba, Ltd. can be used.
無機充填材は、耐湿性向上のため、アミノシラン系カップリング剤、エポキシ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、シラン系カップリング剤、オルガノシラザン化合物、チタネート系カップリング剤などの1種以上の表面処理剤で処理されていることが好ましい。表面処理剤の市販品としては、例えば、信越化学工業(株)製「KBM403」(3−グリシドキシプロピルトリメトキシシラン)、信越化学工業(株)製「KBM803」(3−メルカプトプロピルトリメトキシシラン)、信越化学工業(株)製「KBE903」(3−アミノプロピルトリエトキシシラン)、信越化学工業(株)製「KBM573」(N−フェニル−3−アミノプロピルトリメトキシシラン)、信越化学工業(株)製「SZ−31」(ヘキサメチルジシラザン)等が挙げられる。 The inorganic filler is an inorganic silane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an organosilazane compound, a titanate coupling agent, or the like for improving moisture resistance. It is preferable to be processed by the above surface treatment agent. As a commercial item of a surface treatment agent, Shin-Etsu Chemical Co., Ltd. product "KBM403" (3-glycidoxypropyl trimethoxysilane), Shin-Etsu Chemical Co., Ltd. product "KBM 803" (3-mercapto propyl trimethoxy) is mentioned, for example. Silane), Shin-Etsu Chemical Co., Ltd. “KBE 903” (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. “KBM 573” (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyl disilazane) etc. are mentioned.
また、表面処理剤で表面処理された無機充填材は、溶剤(例えば、メチルエチルケトン(MEK))により洗浄処理した後に、無機充填材の単位表面積当たりのカーボン量を測定することができる。具体的には、溶剤として十分な量のMEKを表面処理剤で表面処理された無機充填材に加えて、25℃で5分間超音波洗浄する。上澄液を除去し、固形分を乾燥させた後、カーボン分析計を用いて無機充填材の単位表面積当たりのカーボン量を測定することができる。カーボン分析計としては、堀場製作所製「EMIA−320V」等を使用することができる。 In addition, after the inorganic filler surface-treated with the surface treatment agent is washed with a solvent (for example, methyl ethyl ketone (MEK)), the amount of carbon per unit surface area of the inorganic filler can be measured. Specifically, a sufficient amount of MEK as a solvent is added to the surface-treated inorganic filler, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solids, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, Horiba "EMIA-320V" etc. can be used.
無機充填材の単位表面積当たりのカーボン量は、無機充填材の分散性向上の観点から、0.02mg/m2以上が好ましく、0.1mg/m2以上がより好ましく、0.2mg/m2以上が更に好ましい。一方、樹脂ワニスの溶融粘度やフィルム形態での溶融粘度の上昇を防止する観点から、1mg/m2以下が好ましく、0.8mg/m2以下がより好ましく、0.5mg/m2以下が更に好ましい。 Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / m 2 or more, 0.1 mg / m 2 or more preferably, 0.2 mg / m 2 The above is more preferable. On the other hand, from the viewpoint of preventing the melt viscosity of the resin varnish and the rise of the melt viscosity in the film form, 1 mg / m 2 or less is preferable, 0.8 mg / m 2 or less is more preferable, and 0.5 mg / m 2 or less preferable.
一実施形態において、熱硬化性樹脂組成物は、上記無機充填材と熱硬化性樹脂を含む。熱硬化性樹脂としては、プリント配線板の絶縁層を形成する際に使用される従来公知の熱硬化性樹脂を用いることができ、中でもエポキシ樹脂が好ましい。熱硬化性樹脂組成物はまた、硬化剤を含んでいてもよい。一実施形態において、熱硬化性樹脂組成物は、無機充填材、エポキシ樹脂及び硬化剤を含む。熱硬化性樹脂組成物は、必要に応じて、さらに熱可塑性樹脂、硬化促進剤、難燃剤及びゴム粒子等の添加剤を含んでいてもよい。
以下、樹脂組成物の材料として使用し得るエポキシ樹脂、硬化剤、及び添加剤について説明する。
In one embodiment, a thermosetting resin composition comprises the above-mentioned inorganic filler and a thermosetting resin. As a thermosetting resin, the conventionally well-known thermosetting resin used when forming the insulating layer of a printed wiring board can be used, Especially, an epoxy resin is preferable. The thermosetting resin composition may also contain a curing agent. In one embodiment, the thermosetting resin composition comprises an inorganic filler, an epoxy resin and a curing agent. The thermosetting resin composition may further contain additives such as a thermoplastic resin, a curing accelerator, a flame retardant, and rubber particles, as necessary.
Hereinafter, the epoxy resin which can be used as a material of a resin composition, a hardening | curing agent, and an additive are demonstrated.
(エポキシ樹脂)
エポキシ樹脂としては、例えば、ビスフェノールA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、ビスフェノールAF型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、トリスフェノールエポキシ樹脂、ナフトールノボラックエポキシ樹脂、フェノールノボラック型エポキシ樹脂、tert-ブチル-カテコール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ナフトール型エポキシ樹脂、アントラセン型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、線状脂肪族エポキシ樹脂、ブタジエン構造を有するエポキシ樹脂、脂環式エポキシ樹脂、複素環式エポキシ樹脂、スピロ環含有エポキシ樹脂、シクロヘキサンジメタノール型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂及びトリメチロール型エポキシ樹脂等が挙げられる。エポキシ樹脂は1種単独で用いてもよく、又は2種以上を併用してもよい。
(Epoxy resin)
As an epoxy resin, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, dicyclopentadiene epoxy resin, trisphenol epoxy resin, naphthol novolac epoxy resin, phenol novolak Type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin Linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin Resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resins and trimethylol type epoxy resins. The epoxy resin may be used singly or in combination of two or more.
エポキシ樹脂は、1分子中に2個以上のエポキシ基を有するエポキシ樹脂を含むことが好ましい。エポキシ樹脂の不揮発成分を100質量%とした場合に、少なくとも50質量%以上は1分子中に2個以上のエポキシ基を有するエポキシ樹脂であるのが好ましい。中でも、1分子中に2個以上のエポキシ基を有し、温度20℃で液状のエポキシ樹脂(以下、「液状エポキシ樹脂」という。)と、1分子中に3個以上のエポキシ基を有し、温度20℃で固体状のエポキシ樹脂(以下、「固体状エポキシ樹脂」という。)とを含むことが好ましい。エポキシ樹脂として、液状エポキシ樹脂と固体状エポキシ樹脂とを併用することで、優れた可撓性を有する熱硬化性樹脂組成物が得られる。また、熱硬化性樹脂組成物を熱硬化して形成される熱硬化体の破断強度も向上する。 The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100% by mass, it is preferable that at least 50% by mass or more is an epoxy resin having two or more epoxy groups in one molecule. Among them, an epoxy resin having two or more epoxy groups in one molecule, a liquid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “liquid epoxy resin”), and three or more epoxy groups in one molecule And a solid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “solid epoxy resin”). By using a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin, a thermosetting resin composition having excellent flexibility can be obtained. Moreover, the breaking strength of the thermosetting body formed by thermosetting the thermosetting resin composition is also improved.
液状エポキシ樹脂としては、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、又はナフタレン型エポキシ樹脂が好ましく、ナフタレン型エポキシ樹脂がより好ましい。液状エポキシ樹脂の具体例としては、DIC(株)製の「HP4032」、「HP4032D」、「EXA4032SS」、「HP4032SS」(ナフタレン型エポキシ樹脂)、三菱化学(株)製の「jER828EL」(ビスフェノールA型エポキシ樹脂)、「jER807」(ビスフェノールF型エポキシ樹脂)、「jER152」(フェノールノボラック型エポキシ樹脂)等が挙げられる。これらは1種単独で用いてもよく、又は2種以上を併用してもよい。 The liquid epoxy resin is preferably a bisphenol A epoxy resin, a bisphenol F epoxy resin, a phenol novolac epoxy resin, or a naphthalene epoxy resin, and more preferably a naphthalene epoxy resin. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “EXA4032SS”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “jER828EL” (bisphenol A manufactured by Mitsubishi Chemical Corporation) Type epoxy resin), “jER 807” (bisphenol F type epoxy resin), “jER 152” (phenol novolac type epoxy resin) and the like. These may be used alone or in combination of two or more.
固体状エポキシ樹脂としては、4官能ナフタレン型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、トリスフェノールエポキシ樹脂、ナフトールノボラックエポキシ樹脂、ビフェニル型エポキシ樹脂、又はナフチレンエーテル型エポキシ樹脂が好ましく、4官能ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、又はナフチレンエーテル型エポキシ樹脂がより好ましい。固体状エポキシ樹脂の具体例としては、DIC(株)製の「HP−4700」、「HP−4710」(4官能ナフタレン型エポキシ樹脂)、「N−690」(クレゾールノボラック型エポキシ樹脂)、「N−695」(クレゾールノボラック型エポキシ樹脂)、「HP−7200」(ジシクロペンタジエン型エポキシ樹脂)、「EXA7311」、「EXA7311−G3」、「HP6000」(ナフチレンエーテル型エポキシ樹脂)、日本化薬(株)製の「EPPN−502H」(トリスフェノールエポキシ樹脂)、「NC7000L」(ナフトールノボラックエポキシ樹脂)、「NC3000H」、「NC3000」、「NC3000L」、「NC3100」(ビフェニル型エポキシ樹脂)、新日鐵化学(株)製の「ESN475」(ナフトールノボラック型エポキシ樹脂)、「ESN485」(ナフトールノボラック型エポキシ樹脂)、三菱化学(株)製の「YX4000H」、「YX4000HK」、「YL6121」(ビフェニル型エポキシ樹脂)等が挙げられる。 As the solid epoxy resin, tetrafunctional naphthalene type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol epoxy resin, naphthol novolac epoxy resin, biphenyl type epoxy resin, or naphthalene ether type epoxy resin Preferably, a tetrafunctional naphthalene type epoxy resin, a biphenyl type epoxy resin, or a naphthylene ether type epoxy resin is more preferable. Specific examples of the solid epoxy resin include “HP-4700”, “HP-4710” (a tetrafunctional naphthalene type epoxy resin), “N-690” (a cresol novolac type epoxy resin), manufactured by DIC Corporation. N-695 "(cresol novolac epoxy resin)," HP-7200 "(dicyclopentadiene epoxy resin)," EXA 7311 "," EXA 7311-G3 "," HP 6000 "(naphthylene epoxy resin), Nipponized Drug "EPPN-502H" (trisphenol epoxy resin), "NC7000L" (naphthol novolac epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl epoxy resin), “ESN 475” manufactured by Nippon Steel Chemical Co., Ltd. Tall novolak epoxy resin), "ESN485" (naphthol novolak type epoxy resin), "YX4000H" manufactured by Mitsubishi Chemical Corporation, "YX4000HK", "YL6121" (biphenyl type epoxy resin) and the like.
エポキシ樹脂として、液状エポキシ樹脂と固体状エポキシ樹脂とを併用する場合、それらの量比(液状エポキシ樹脂:固体状エポキシ樹脂)は、質量比で、1:0.1〜1:4の範囲が好ましい。液状エポキシ樹脂と固体状エポキシ樹脂との量比を斯かる範囲とすることにより、i)後述する接着フィルムの形態で使用する場合に適度な粘着性がもたらされる、ii)接着フィルムの形態で使用する場合に十分な可撓性が得られ、取り扱い性が向上する、並びにiii)十分な破断強度を有する硬化体を得ることができるなどの効果が得られる。上記i)〜iii)の効果の観点から、液状エポキシ樹脂と固体状エポキシ樹脂の量比(液状エポキシ樹脂:固体状エポキシ樹脂)は、質量比で、1:0.3〜1:3.5の範囲がより好ましく、1:0.6〜1:3の範囲がさらに好ましく、1:0.8〜1:2.6の範囲が特に好ましい。 When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, the mass ratio (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1: 4 in mass ratio. preferable. By setting the ratio of the liquid epoxy resin to the solid epoxy resin in such a range, i) suitable adhesiveness is provided when used in the form of an adhesive film described later, ii) used in the form of an adhesive film In this case, sufficient flexibility can be obtained, the handling property is improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii), the mass ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is 1: 0.3 to 1: 3.5 in mass ratio Is more preferable, the range of 1: 0.6 to 1: 3 is more preferable, and the range of 1: 0.8 to 1: 2.6 is particularly preferable.
熱硬化性樹脂組成物中のエポキシ樹脂の含有量は、3質量%〜50質量%が好ましく、5質量%〜45質量%がより好ましく、5質量%〜40質量%が更に好ましく、7質量%〜35質量%が特に好ましい。 3 mass%-50 mass% are preferable, as for content of the epoxy resin in a thermosetting resin composition, 5 mass%-45 mass% are more preferable, 5 mass%-40 mass% are still more preferable, and 7 mass%. -35 mass% is particularly preferred.
(硬化剤)
硬化剤としては、エポキシ樹脂を硬化する機能を有する限り特に限定されないが、例えば、フェノール系硬化剤、ナフトール系硬化剤、活性エステル系硬化剤、ベンゾオキサジン系硬化剤、及びシアネートエステル系硬化剤が挙げられる。硬化剤は1種単独で用いてもよく、又は2種以上を併用してもよい。
(Hardening agent)
The curing agent is not particularly limited as long as it has a function of curing an epoxy resin, but for example, a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, and a cyanate ester-based curing agent It can be mentioned. A hardening agent may be used individually by 1 type, or may use 2 or more types together.
フェノール系硬化剤及びナフトール系硬化剤としては、耐熱性及び耐水性の観点から、ノボラック構造を有するフェノール系硬化剤、又はノボラック構造を有するナフトール系硬化剤が好ましい。また、導体層との密着性(剥離強度)の観点から、含窒素フェノール系硬化剤が好ましく、トリアジン骨格含有フェノール系硬化剤がより好ましい。中でも、耐熱性、耐水性、及び導体層との密着性(剥離強度)を高度に満足させる観点から、トリアジン骨格含有フェノールノボラック樹脂を硬化剤として用いることが好ましい。 From the viewpoints of heat resistance and water resistance, as the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolac structure or a naphthol-based curing agent having a novolac structure is preferable. Further, from the viewpoint of adhesion (peeling strength) to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Among them, it is preferable to use a triazine skeleton-containing phenol novolac resin as a curing agent from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion (peeling strength) with a conductor layer.
フェノール系硬化剤及びナフトール系硬化剤の具体例としては、例えば、明和化成(株)製の「MEH−7700」、「MEH−7810」、「MEH−7851」、日本化薬(株)製の「NHN」、「CBN」、「GPH」、東都化成(株)製の「SN170」、「SN180」、「SN190」、「SN475」、「SN485」、「SN495」、「SN375」、「SN395」、DIC(株)製の「LA7052」、「LA7054」、「LA3018」、群栄化学工業(株)製の「GDP−6140」等が挙げられる。 Specific examples of the phenolic curing agent and naphthol curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7851” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395" manufactured by Tohto Kasei Co., Ltd. And “GDP-6140” manufactured by DIC Corporation, “LA7052”, “LA7054”, “LA3018”, and Gunei Chemical Industry Co., Ltd., and the like.
導体層との密着性(剥離強度)の観点から、活性エステル系硬化剤も好ましい。詳細は後述することとするが、活性エステル系硬化剤を使用することにより、熱硬化性樹脂組成物を熱硬化させる際の温度条件が「ノンステップ」条件や「ステップ」条件であっても、所望の引っかき硬度を有する熱硬化体を容易に得ることができ、表面のSi原子とO原子の割合が所望の範囲にある粗化硬化体を簡便に実現できる。 From the viewpoint of adhesion (peel strength) to the conductor layer, active ester curing agents are also preferable. Although details will be described later, it is desirable to use an active ester-based curing agent even if the temperature conditions for thermosetting the thermosetting resin composition are “non-step” conditions or “step” conditions. It is possible to easily obtain a thermosetting body having a scratch hardness and easily realize a roughening hardened body in which the ratio of Si atoms to O atoms on the surface is in a desired range.
活性エステル系硬化剤としては、特に制限はないが、一般にフェノールエステル類、チオフェノールエステル類、N−ヒドロキシアミンエステル類、複素環ヒドロキシ化合物のエステル類等の反応活性の高いエステル基を1分子中に2個以上有する化合物が好ましく用いられる。当該活性エステル系硬化剤は、カルボン酸化合物及び/又はチオカルボン酸化合物とヒドロキシ化合物及び/又はチオール化合物との縮合反応によって得られるものが好ましい。特に耐熱性向上の観点から、カルボン酸化合物とヒドロキシ化合物とから得られる活性エステル系硬化剤が好ましく、カルボン酸化合物とフェノール化合物及び/又はナフトール化合物とから得られる活性エステル系硬化剤がより好ましい。カルボン酸化合物としては、例えば安息香酸、酢酸、コハク酸、マレイン酸、イタコン酸、フタル酸、イソフタル酸、テレフタル酸、ピロメリット酸等が挙げられる。フェノール化合物又はナフトール化合物としては、例えば、ハイドロキノン、レゾルシン、ビスフェノールA、ビスフェノールF、ビスフェノールS、フェノールフタリン、メチル化ビスフェノールA、メチル化ビスフェノールF、メチル化ビスフェノールS、フェノール、o−クレゾール、m−クレゾール、p−クレゾール、カテコール、α−ナフトール、β−ナフトール、1,5−ジヒドロキシナフタレン、1,6−ジヒドロキシナフタレン、2,6−ジヒドロキシナフタレン、ジヒドロキシベンゾフェノン、トリヒドロキシベンゾフェノン、テトラヒドロキシベンゾフェノン、フロログルシン、ベンゼントリオール、ジシクロペンタジエニルジフェノール、フェノールノボラック等が挙げられる。 The active ester curing agent is not particularly limited, but generally an ester group having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters and esters of heterocyclic hydroxy compounds is contained in one molecule. Compounds having two or more of them are preferably used. The active ester curing agent is preferably obtained by condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid. As a phenol compound or naphthol compound, for example, hydroquinone, resorcine, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzene triol, dicyclopentadienyl diphenol, phenol novolac and the like can be mentioned.
活性エステル系硬化剤としては、ジシクロペンタジエニルジフェノール構造を含む活性エステル化合物、ナフタレン構造を含む活性エステル化合物、フェノールノボラックのアセチル化物を含む活性エステル化合物、フェノールノボラックのベンゾイル化物を含む活性エステル化合物が好ましく、中でもナフタレン構造を含む活性エステル化合物、ジシクロペンタジエニルジフェノール構造を含む活性エステル化合物がより好ましい。 As an active ester curing agent, an active ester compound containing a dicyclopentadienyl diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated compound of phenol novolac, an active ester containing benzoylated compound of phenol novolac Compounds are preferable, and active ester compounds containing a naphthalene structure, and active ester compounds containing a dicyclopentadienyl diphenol structure are more preferable.
活性エステル系硬化剤の市販品としては、ジシクロペンタジエニルジフェノール構造を含む活性エステル化合物として、「EXB9451」、「EXB9460」、「EXB9460S」、「HPC−8000−65T」(DIC(株)製)、ナフタレン構造を含む活性エステル化合物として「EXB9416−70BK」(DIC(株)製)、フェノールノボラックのアセチル化物を含む活性エステル化合物として「DC808」(三菱化学(株)製)、フェノールノボラックのベンゾイル化物を含む活性エステル化合物として「YLH1026」(三菱化学(株)製)などが挙げられる。 As a commercial item of the active ester-based curing agent, as an active ester compound having a dicyclopentadienyl diphenol structure, “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T” (DIC Corporation) Products), “EXB9416-70BK” (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, “DC808” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing acetylated products of phenol novolac, phenol novolac Examples of the active ester compound containing a benzoyl compound include “YLH1026” (manufactured by Mitsubishi Chemical Corporation).
ベンゾオキサジン系硬化剤の具体例としては、昭和高分子(株)製の「HFB2006M」、四国化成工業(株)製の「P−d」、「F−a」が挙げられる。 Specific examples of the benzoxazine-based curing agent include “HFB 2006 M” manufactured by Showa Highpolymer Co., Ltd., “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.
シアネートエステル系硬化剤としては、例えば、ビスフェノールAジシアネート、ポリフェノールシアネート(オリゴ(3−メチレン−1,5−フェニレンシアネート)、4,4’−メチレンビス(2,6−ジメチルフェニルシアネート)、4,4’−エチリデンジフェニルジシアネート、ヘキサフルオロビスフェノールAジシアネート、2,2−ビス(4−シアネート)フェニルプロパン、1,1−ビス(4−シアネートフェニルメタン)、ビス(4−シアネート−3,5−ジメチルフェニル)メタン、1,3−ビス(4−シアネートフェニル−1−(メチルエチリデン))ベンゼン、ビス(4−シアネートフェニル)チオエーテル、及びビス(4−シアネートフェニル)エーテル等の2官能シアネート樹脂、フェノールノボラック及びクレゾールノボラック等から誘導される多官能シアネート樹脂、これらシアネート樹脂が一部トリアジン化したプレポリマーなどが挙げられる。シアネートエステル系硬化剤の具体例としては、ロンザジャパン(株)製の「PT30」及び「PT60」(いずれもフェノールノボラック型多官能シアネートエステル樹脂)、「BA230」(ビスフェノールAジシアネートの一部又は全部がトリアジン化され三量体となったプレポリマー)等が挙げられる。 As a cyanate ester-based curing agent, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylene bis (2,6-dimethylphenyl cyanate), 4,4 '-Ethylidene diphenyl dicyanate, hexafluoro bisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1, 1-bis (4- cyanate phenyl methane), bis (4- cyanate 3,5- dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatophenyl-1- (methylethylidene)) benzene, bis (4-cyanatophenyl) thioether, and bis (4-cyanatophenyl) ether, phenol Novolak and Ku Polyfunctional cyanate resins derived from zol novolac etc., prepolymers in which these cyanate resins are partially triazineated, etc. Specific examples of cyanate ester-based curing agents include “PT30” manufactured by Lonza Japan Co., Ltd. and "PT60" (all are phenol novolac type polyfunctional cyanate ester resins), "BA 230" (a prepolymer in which a part or all of bisphenol A dicyanate is triazinated to form a trimer), and the like.
エポキシ樹脂と硬化剤との量比は、[エポキシ樹脂のエポキシ基の合計数]:[硬化剤の反応基の合計数]の比率で、1:0.2〜1:2の範囲が好ましく、1:0.3〜1:1.5がより好ましく、1:0.4〜1:1が更に好ましい。ここで、硬化剤の反応基とは、活性水酸基、活性エステル基等であり、硬化剤の種類によって異なる。また、エポキシ樹脂のエポキシ基の合計数とは、各エポキシ樹脂の固形分質量をエポキシ当量で除した値をすべてのエポキシ樹脂について合計した値であり、硬化剤の反応基の合計数とは、各硬化剤の固形分質量を反応基当量で除した値をすべての硬化剤について合計した値である。エポキシ樹脂と硬化剤との量比を斯かる範囲とすることにより、熱硬化性樹脂組成物の熱硬化体の耐熱性がより向上する。 The ratio by weight of the epoxy resin to the curing agent is preferably in the range of 1: 0.2 to 1: 2, as a ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of curing agent], 1: 0.3 to 1: 1.5 is more preferable, and 1: 0.4 to 1: 1 is further preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, or the like, which differs depending on the type of the curing agent. Further, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the mass of the solid content of each epoxy resin by the epoxy equivalent, for all the epoxy resins, and the total number of reactive groups of the curing agent is It is the value which totaled the value which remove | divided the solid content mass of each hardening | curing agent by reaction group equivalent for all the hardening | curing agents. By setting the ratio of the epoxy resin to the curing agent in such a range, the heat resistance of the thermosetting body of the thermosetting resin composition is further improved.
一実施形態において、本発明の粗化硬化体を形成するために使用する熱硬化性樹脂組成物は、上述の無機充填材、エポキシ樹脂、及び硬化剤を含む。熱硬化性樹脂組成物は、無機充填材としてシリカを、エポキシ樹脂として液状エポキシ樹脂と固体状エポキシ樹脂との混合物(液状エポキシ樹脂:固体状エポキシ樹脂の質量比は1:0.1〜1:4の範囲が好ましく、1:0.3〜1:3.5の範囲がより好ましく、1:0.6〜1:3の範囲がさらに好ましく、1:0.8〜1:2.6の範囲が特に好ましい)を、硬化剤としてフェノール系硬化剤、ナフトール系硬化剤及び活性エステル系硬化剤からなる群から選択される1種以上を、それぞれ含むことが好ましい。斯かる特定の成分を組み合わせて含む熱硬化性樹脂組成物層に関しても、無機充填材、エポキシ樹脂、及び硬化剤の好適な含有量は上述のとおりであるが、中でも、無機充填材の含有量が50質量%〜95質量%、エポキシ樹脂の含有量が3質量%〜50質量%であることが好ましく、無機充填材の含有量が50質量%〜90質量%、エポキシ樹脂の含有量が5質量%〜45質量%であることがより好ましい。硬化剤の含有量に関しては、エポキシ樹脂のエポキシ基の合計数と、硬化剤の反応基の合計数との比が、好ましくは1:0.2〜1:2の範囲、より好ましくは1:0.3〜1:1.5の範囲、さらに好ましくは1:0.4〜1:1の範囲となるように含有させる。 In one embodiment, the thermosetting resin composition used to form the roughened cured product of the present invention comprises the above-described inorganic filler, an epoxy resin, and a curing agent. The thermosetting resin composition contains silica as an inorganic filler, a mixture of a liquid epoxy resin and a solid epoxy resin as an epoxy resin (the mass ratio of liquid epoxy resin: solid epoxy resin is 1: 0.1 to 1: 1: The range of 4 is preferable, the range of 1: 0.3 to 1: 3.5 is more preferable, the range of 1: 0.6 to 1: 3 is more preferable, and 1: 0.8 to 1: 2.6. It is preferable to include one or more selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent, and an active ester-based curing agent as the curing agent. With regard to the thermosetting resin composition layer containing such specific components in combination, the preferred content of the inorganic filler, the epoxy resin, and the curing agent is as described above, but above all, the content of the inorganic filler Is preferably 50% by mass to 95% by mass, the content of the epoxy resin is preferably 3% by mass to 50% by mass, the content of the inorganic filler is 50% by mass to 90% by mass, the content of the epoxy resin is 5 It is more preferable that it is mass%-45 mass%. Regarding the content of the curing agent, the ratio of the total number of epoxy groups of the epoxy resin to the total number of reactive groups of the curing agent is preferably in the range of 1: 0.2 to 1: 2, more preferably 1: It is contained so as to be in the range of 0.3 to 1: 1.5, more preferably in the range of 1: 0.4 to 1: 1.
熱硬化性樹脂組成物は、必要に応じて、さらに熱可塑性樹脂、硬化促進剤、難燃剤及びゴム粒子等の添加剤を含んでいてもよい。 The thermosetting resin composition may further contain additives such as a thermoplastic resin, a curing accelerator, a flame retardant, and rubber particles, as necessary.
(熱可塑性樹脂)
表面のSi原子とO原子の割合が所望の範囲にある粗化硬化体を容易に実現できる観点から、熱硬化性樹脂組成物は、熱可塑性樹脂を含むことが好ましい。熱可塑性樹脂としては、例えば、フェノキシ樹脂、ポリビニルアセタール樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリエーテルスルホン樹脂、及びポリスルホン樹脂等が挙げられ、中でも、フェノキシ樹脂、ポリビニルアセタール樹脂が好ましい。熱可塑性樹脂は1種単独で用いてもよく、又は2種以上を併用してもよい。
(Thermoplastic resin)
It is preferable that the thermosetting resin composition contains a thermoplastic resin from the viewpoint of easily realizing a roughened cured product in which the ratio of Si atoms to O atoms on the surface is in a desired range. Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamide imide resin, polyether sulfone resin, and polysulfone resin. Among these, phenoxy resin and polyvinyl acetal resin are preferable. The thermoplastic resin may be used alone or in combination of two or more.
熱可塑性樹脂のポリスチレン換算の重量平均分子量は8,000〜70,000の範囲が好ましく、10,000〜60,000の範囲がより好ましく、20,000〜60,000の範囲が更に好ましい。熱可塑性樹脂のポリスチレン換算の重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)法で測定される。具体的には、熱可塑性樹脂のポリスチレン換算の重量平均分子量は、測定装置として(株)島津製作所製LC−9A/RID−6Aを、カラムとして昭和電工(株)製Shodex K−800P/K−804L/K−804Lを、移動相としてクロロホルム等を用いて、カラム温度40℃にて測定し、標準ポリスチレンの検量線を用いて算出することができる。 The weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000. The polystyrene equivalent weight average molecular weight of the thermoplastic resin is measured by gel permeation chromatography (GPC). Specifically, the polystyrene equivalent weight average molecular weight of the thermoplastic resin can be measured by using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804 L / K-804 L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and calculated using a standard polystyrene calibration curve.
フェノキシ樹脂としては、例えば、ビスフェノールA骨格、ビスフェノールF骨格、ビスフェノールS骨格、ビスフェノールアセトフェノン骨格、ノボラック骨格、ビフェニル骨格、フルオレン骨格、ジシクロペンタジエン骨格、ノルボルネン骨格、ナフタレン骨格、アントラセン骨格、アダマンタン骨格、テルペン骨格、及びトリメチルシクロヘキサン骨格からなる群から選択される1種以上の骨格を有するフェノキシ樹脂が挙げられる。フェノキシ樹脂の末端は、フェノール性水酸基、エポキシ基等のいずれの官能基でもよい。フェノキシ樹脂は1種単独で用いてもよく、又は2種以上を併用してもよい。フェノキシ樹脂の具体例としては、三菱化学(株)製の「1256」及び「4250」(いずれもビスフェノールA骨格含有フェノキシ樹脂)、「YX8100」(ビスフェノールS骨格含有フェノキシ樹脂)、及び「YX6954」(ビスフェノールアセトフェノン骨格含有フェノキシ樹脂)が挙げられ、その他にも、東都化成(株)製の「FX280」及び「FX293」、三菱化学(株)製の「YL7553」、「YL6794」、「YL7213」、「YL7290」及び「YL7482」等が挙げられる。 As the phenoxy resin, for example, bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene The phenoxy resin which has 1 or more types of frame | skeleton selected from frame | skeleton, and the group which consists of trimethyl cyclohexane frame | skeleton is mentioned. The terminal of the phenoxy resin may be any functional group such as phenolic hydroxyl group and epoxy group. A phenoxy resin may be used individually by 1 type, or may use 2 or more types together. Specific examples of the phenoxy resin include “1256” and “4250” (both of which are bisphenol A skeleton-containing phenoxy resins), “YX8100” (bisphenol S skeleton-containing phenoxy resins), and “YX6954” (manufactured by Mitsubishi Chemical Corporation). Other examples include “FX280” and “FX293” manufactured by Tohto Kasei Co., Ltd., “YL7553” manufactured by Mitsubishi Chemical Corporation, “YL6794”, “YL7213”, and the like. YL7290 "and" YL7482 "can be mentioned.
ポリビニルアセタール樹脂としては、ポリビニルブチラール樹脂が好ましく、その具体例としては、電気化学工業(株)製の電化ブチラール4000−2、5000−A、6000−C、6000−EP、積水化学工業(株)製のエスレックBHシリーズ、BXシリーズ、KSシリーズ、BLシリーズ、BMシリーズ等が挙げられる。 As polyvinyl acetal resin, polyvinyl butyral resin is preferable, As a specific example, electrified butyral 4000-2, 5000-A, 6000-C, 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd., Sekisui Chemical Co., Ltd. Elek BH series, BX series, KS series, BL series, BM series etc.
ポリイミド樹脂の具体例としては、新日本理化(株)製の「リカコートSN20」及び「リカコートPN20」が挙げられる。ポリイミド樹脂の具体例としてはまた、2官能性ヒドロキシル基末端ポリブタジエン、ジイソシアネート化合物及び四塩基酸無水物を反応させて得られる線状ポリイミド(特開2006−37083号公報記載のもの)、ポリシロキサン骨格含有ポリイミド(特開2002−12667号公報及び特開2000−319386号公報等に記載のもの)等の変性ポリイミドが挙げられる。 As a specific example of a polyimide resin, Shin-Nika Chemical Co., Ltd. "Rika coat SN20" and "Rika coat PN20" are mentioned. Specific examples of the polyimide resin also include a linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (described in JP-A-2006-37083), and a polysiloxane skeleton Modified polyimides such as contained polyimides (described in JP-A-2002-12667 and JP-A-2000-319386) may, for example, be mentioned.
ポリアミドイミド樹脂の具体例としては、東洋紡績(株)製の「バイロマックスHR11NN」及び「バイロマックスHR16NN」が挙げられる。ポリアミドイミド樹脂の具体例としてはまた、日立化成工業(株)製のポリシロキサン骨格含有ポリアミドイミド「KS9100」、「KS9300」等の変性ポリアミドイミドが挙げられる。 As a specific example of a polyamide imide resin, Toyobo Co., Ltd. product "Viromax HR11NN" and "Viromax HR16NN" are mentioned. Specific examples of the polyamideimide resin also include modified polyamideimides such as polysiloxane skeleton-containing polyamideimide "KS9100" and "KS9300" manufactured by Hitachi Chemical Co., Ltd.
ポリエーテルスルホン樹脂の具体例としては、住友化学(株)製の「PES5003P」等が挙げられる。 As a specific example of polyether sulfone resin, Sumitomo Chemical Co., Ltd. "PES5003P" etc. are mentioned.
ポリスルホン樹脂の具体例としては、ソルベイアドバンストポリマーズ(株)製のポリスルホン「P1700」、「P3500」等が挙げられる。 Specific examples of the polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.
表面のSi原子とO原子の割合が所望の範囲にある粗化硬化体を容易に実現できる観点から、熱硬化性樹脂組成物中の熱可塑性樹脂の含有量は、0.1質量%〜20質量%であることが好ましく、0.5質量%〜10質量%であることがより好ましい。 The content of the thermoplastic resin in the thermosetting resin composition is 0.1% by mass to 20%, from the viewpoint of easily realizing a roughened cured product in which the ratio of Si atoms to O atoms on the surface is in a desired range. It is preferable that it is mass%, and it is more preferable that it is 0.5 mass%-10 mass%.
硬化促進剤としては、例えば、リン系硬化促進剤、アミン系硬化促進剤、イミダゾール系硬化促進剤、グアニジン系硬化促進剤等が挙げられる。表面のSi原子とO原子の割合が所望の範囲にある粗化硬化体を容易に実現できる観点から、硬化促進剤としては、アミン系硬化促進剤、イミダゾール系硬化促進剤がより好ましい。 As a curing accelerator, a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, etc. are mentioned, for example. From the viewpoint of easily achieving a roughened cured product in which the ratio of Si atoms to O atoms on the surface is in a desired range, amine curing accelerators and imidazole curing accelerators are more preferable as the curing accelerator.
リン系硬化促進剤としては、例えば、トリフェニルホスフィン、ホスホニウムボレート化合物、テトラフェニルホスホニウムテトラフェニルボレート、n−ブチルホスホニウムテトラフェニルボレート、テトラブチルホスホニウムデカン酸塩、(4−メチルフェニル)トリフェニルホスホニウムチオシアネート、テトラフェニルホスホニウムチオシアネート、ブチルトリフェニルホスホニウムチオシアネート等が挙げられる。 As a phosphorus-based curing accelerator, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate Tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate and the like.
アミン系硬化促進剤としては、例えば、トリエチルアミン、トリブチルアミンなどのトリアルキルアミン、4−ジメチルアミノピリジン、ベンジルジメチルアミン、2,4,6,−トリス(ジメチルアミノメチル)フェノール、1,8−ジアザビシクロ(5,4,0)−ウンデセン等が挙げられ、4−ジメチルアミノピリジン、1,8−ジアザビシクロ(5,4,0)−ウンデセンが好ましい。 Examples of the amine-based curing accelerator include triethylamine, trialkylamines such as tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo Examples include (5,4,0) -undecene and the like, with preference given to 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene.
イミダゾール系硬化促進剤としては、例えば、2−メチルイミダゾール、2−ウンデシルイミダゾール、2−ヘプタデシルイミダゾール、1,2−ジメチルイミダゾール、2−エチル−4−メチルイミダゾール、1,2−ジメチルイミダゾール、2−エチル−4−メチルイミダゾール、2−フェニルイミダゾール、2−フェニル−4−メチルイミダゾール、1−ベンジル−2−メチルイミダゾール、1−ベンジル−2−フェニルイミダゾール、1−シアノエチル−2−メチルイミダゾール、1−シアノエチル−2−ウンデシルイミダゾール、 1−シアノエチル−2−エチル−4−メチルイミダゾール、1−シアノエチル−2−フェニルイミダゾール、1−シアノエチル−2−ウンデシルイミダゾリウムトリメリテイト、1−シアノエチル−2−フェニルイミダゾリウムトリメリテイト、2,4−ジアミノ−6−[2’−メチルイミダゾリル−(1’)]−エチル−s−トリアジン、2,4−ジアミノ−6−[2’−ウンデシルイミダゾリル−(1’)]−エチル−s−トリアジン、2,4−ジアミノ−6−[2’−エチル−4’−メチルイミダゾリル−(1’)]−エチル−s−トリアジン、2,4−ジアミノ−6−[2’−メチルイミダゾリル−(1’)]−エチル−s−トリアジンイソシアヌル酸付加物、2−フェニルイミダゾールイソシアヌル酸付加物、2−フェニル−4,5−ジヒドロキシメチルイミダゾール、2−フェニル−4−メチル−5ヒドロキシメチルイミダゾール、2,3−ジヒドロ−1H−ピロロ[1,2−a]ベンズイミダゾール、1−ドデシル−2−メチル−3−ベンジルイミダゾリウムクロライド、2−メチルイミダゾリン、2−フェニルイミダゾリン等のイミダゾール化合物及びイミダゾール化合物とエポキシ樹脂とのアダクト体が挙げられ、2−エチル−4−メチルイミダゾール、1−ベンジル−2−フェニルイミダゾールが好ましい。 Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- -Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl -(1 ')-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino -6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl -4-Methyl-5 hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyone And imidazole compounds such as 3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and adducts of the imidazole compound with an epoxy resin, and 2-ethyl-4-methylimidazole, 1-benzyl-2-ylimidazole. Phenylimidazole is preferred.
グアニジン系硬化促進剤としては、例えば、ジシアンジアミド、1−メチルグアニジン、1−エチルグアニジン、1−シクロヘキシルグアニジン、1−フェニルグアニジン、1−(o−トリル)グアニジン、ジメチルグアニジン、ジフェニルグアニジン、トリメチルグアニジン、テトラメチルグアニジン、ペンタメチルグアニジン、1,5,7−トリアザビシクロ[4.4.0]デカ−5−エン、7−メチル−1,5,7−トリアザビシクロ[4.4.0]デカ−5−エン、1−メチルビグアニド、1−エチルビグアニド、1−n−ブチルビグアニド、1−n−オクタデシルビグアニド、1,1−ジメチルビグアニド、1,1−ジエチルビグアニド、1−シクロヘキシルビグアニド、1−アリルビグアニド、1−フェニルビグアニド、1−(o−トリル)ビグアニド等が挙げられる。 As the guanidine-based curing accelerator, for example, dicyandiamide, 1-methyl guanidine, 1-ethyl guanidine, 1-cyclohexyl guanidine, 1-phenyl guanidine, 1- (o-tolyl) guanidine, dimethyl guanidine, diphenyl guanidine, trimethyl guanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1-( - tolyl) biguanide, and the like.
硬化促進剤は、1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。好適な一実施形態において、熱効果性樹脂組成物に含有される硬化促進剤は、アミン系硬化促進剤及びイミダゾール系硬化促進剤からなる群から選択される1種以上である。熱硬化性樹脂組成物中の硬化促進剤の含有量は、エポキシ樹脂と硬化剤の不揮発成分合計量を100質量%としたとき、0.05質量%〜3質量%の範囲で使用することが好ましい。 The curing accelerator may be used alone or in combination of two or more. In a preferred embodiment, the curing accelerator contained in the heat-effect resin composition is at least one selected from the group consisting of an amine curing accelerator and an imidazole curing accelerator. The content of the curing accelerator in the thermosetting resin composition may be in the range of 0.05% by mass to 3% by mass, based on 100% by mass of the total of the non-volatile components of the epoxy resin and the curing agent. preferable.
難燃剤としては、例えば、有機リン系難燃剤、有機系窒素含有リン化合物、窒素化合物、シリコーン系難燃剤、金属水酸化物等が挙げられる。難燃剤は1種単独で用いてもよく、又は2種以上を併用してもよい。熱硬化性樹脂組成物層中の難燃剤の含有量は特に限定はされないが、0.5質量%〜10質量%が好ましく、1質量%〜9質量%がより好ましく、1.5質量%〜8質量%が更に好ましい。 Examples of the flame retardant include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, metal hydroxides and the like. The flame retardant may be used alone or in combination of two or more. The content of the flame retardant in the thermosetting resin composition layer is not particularly limited, but is preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 9% by mass, and 1.5% by mass or more 8 mass% is more preferable.
ゴム粒子としては、例えば、後述する有機溶剤に溶解せず、上述のエポキシ樹脂、硬化剤、及び熱可塑性樹脂などとも相溶しないものが使用される。このようなゴム粒子は、一般には、ゴム成分の分子量を有機溶剤や樹脂に溶解しないレベルまで大きくし、粒子状とすることで調製される。 As the rubber particles, for example, those which do not dissolve in an organic solvent described later and are not compatible with the above-described epoxy resin, curing agent, thermoplastic resin and the like are used. Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level at which the rubber component does not dissolve in an organic solvent or resin, and forming it into particles.
ゴム粒子としては、例えば、コアシェル型ゴム粒子、架橋アクリロニトリルブタジエンゴム粒子、架橋スチレンブタジエンゴム粒子、アクリルゴム粒子などが挙げられる。コアシェル型ゴム粒子は、コア層とシェル層とを有するゴム粒子であり、例えば、外層のシェル層がガラス状ポリマーで構成され、内層のコア層がゴム状ポリマーで構成される2層構造、又は外層のシェル層がガラス状ポリマーで構成され、中間層がゴム状ポリマーで構成され、コア層がガラス状ポリマーで構成される3層構造のものなどが挙げられる。ガラス状ポリマー層は、例えば、メチルメタクリレート重合物などで構成され、ゴム状ポリマー層は、例えば、ブチルアクリレート重合物(ブチルゴム)などで構成される。ゴム粒子は1種単独で用いてもよく、又は2種以上を併用してもよい。 Examples of the rubber particles include core-shell rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell rubber particles are rubber particles having a core layer and a shell layer, and for example, a two-layer structure in which the shell layer of the outer layer is composed of a glassy polymer and the core layer of the inner layer is composed of a rubbery polymer, The shell layer of the outer layer is composed of a glassy polymer, the middle layer is composed of a rubbery polymer, and the core layer is composed of a glassy polymer. The glassy polymer layer is composed of, for example, methyl methacrylate polymer and the like, and the rubbery polymer layer is composed of, for example, butyl acrylate polymer (butyl rubber) and the like. The rubber particles may be used alone or in combination of two or more.
ゴム粒子の平均粒径は、好ましくは0.005μm〜1μmの範囲であり、より好ましくは0.2μm〜0.6μmの範囲である。ゴム粒子の平均粒径は、動的光散乱法を用いて測定することができる。例えば、適当な有機溶剤にゴム粒子を超音波などにより均一に分散させ、濃厚系粒径アナライザー(FPAR−1000;大塚電子(株)製)を用いて、ゴム粒子の粒度分布を質量基準で作成し、そのメディアン径を平均粒径とすることで測定することができる。熱硬化性樹脂組成物中のゴム粒子の含有量は、好ましくは1質量%〜10質量%であり、より好ましくは2質量%〜5質量%である。 The average particle size of the rubber particles is preferably in the range of 0.005 μm to 1 μm, and more preferably in the range of 0.2 μm to 0.6 μm. The average particle size of the rubber particles can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in a suitable organic solvent by ultrasonic waves or the like, and the particle size distribution of rubber particles is made based on mass using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.) It can measure by making the median diameter into an average particle diameter. The content of rubber particles in the thermosetting resin composition is preferably 1% by mass to 10% by mass, and more preferably 2% by mass to 5% by mass.
本発明の粗化硬化体を形成するために使用する熱硬化性樹脂組成物は、必要に応じて、他の添加剤を含んでいてもよく、斯かる他の添加剤としては、例えば、有機銅化合物、有機亜鉛化合物及び有機コバルト化合物等の有機金属化合物、並びに有機フィラー、増粘剤、消泡剤、レベリング剤、密着性付与剤、着色剤及び硬化性樹脂等の樹脂添加剤等が挙げられる。 The thermosetting resin composition used to form the roughened cured product of the present invention may optionally contain other additives, and as such other additives, for example, organic Organic metal compounds such as copper compounds, organic zinc compounds and organic cobalt compounds, and resin additives such as organic fillers, thickeners, antifoaming agents, leveling agents, adhesion imparting agents, coloring agents, and curable resins are listed. Be
本発明の粗化硬化体は、プリント配線板の絶縁層を形成するための粗化硬化体(プリント配線板の絶縁層用粗化硬化体)として使用することができる。中でも、ビルドアップ方式によるプリント配線板の製造において、絶縁層を形成するための粗化硬化体(プリント配線板のビルドアップ絶縁層用粗化硬化体)として好適に使用することができ、メッキにより導体層を形成するための硬化体(メッキにより導体層を形成するプリント配線板のビルドアップ絶縁層用粗化硬化体)としてさらに好適に使用することができる。 The roughened cured body of the present invention can be used as a roughened cured body (roughened cured body for insulating layer of printed wiring board) for forming the insulating layer of the printed wiring board. Among them, in the manufacture of a printed wiring board by a build-up method, it can be suitably used as a roughened cured body (roughened cured body for a build-up insulating layer of a printed wiring board) for forming an insulating layer. It can be more preferably used as a cured product for forming a conductor layer (roughed cured product for a buildup insulating layer of a printed wiring board on which a conductor layer is formed by plating).
プリント配線板に本発明の粗化硬化体を使用する場合、本発明の粗化硬化体を形成するために使用する熱硬化性樹脂組成物は、回路基板への積層を簡便かつ効率よく実施できる観点から、該熱硬化性樹脂組成物からなる層を含む接着フィルムの形態で用いることが好適である。 When the roughened cured product of the present invention is used for a printed wiring board, the thermosetting resin composition used to form the roughened cured product of the present invention can be easily and efficiently laminated on a circuit board From the viewpoint, it is preferable to use in the form of an adhesive film including a layer made of the thermosetting resin composition.
一実施形態において、接着フィルムは、支持体と、該支持体と接合している熱硬化性樹脂組成物層(接着層)とを含んでなる。 In one embodiment, the adhesive film comprises a support and a thermosetting resin composition layer (adhesive layer) bonded to the support.
なお、複層構造の粗化硬化体を形成するために、複層構造の熱硬化性樹脂組成物層を使用してよい。この場合、熱硬化性樹脂組成物層全体として無機充填材含有量が50質量%以上であればよい。 In addition, in order to form the roughening hardened body of a multilayer structure, you may use the thermosetting resin composition layer of a multilayer structure. In this case, the content of the inorganic filler may be 50% by mass or more in the entire thermosetting resin composition layer.
支持体としては、プラスチック材料からなるフィルムが好適に用いられる。プラスチック材料としては、例えば、ポリエチレンテレフタレート(以下、「PET」と略称することがある。)、ポリエチレンナフタレート(以下、「PEN」と略称することがある。)等のポリエステル、ポリカーボネート(以下、「PC」と略称することがある。)、ポリメチルメタクリレート(PMMA)等のアクリル、環状ポリオレフィン、トリアセチルセルロース(TAC)、ポリエーテルサルファイド(PES)、ポリエーテルケトン、ポリイミドなどが挙げられる。中でも、ポリエチレンテレフタレート、ポリエチレンナフタレートが好ましく、安価なポリエチレンテレフタレートが特に好ましい。好適な一実施形態において、支持体は、ポリエチレンテレフタレートフィルムである。 As the support, a film made of a plastic material is suitably used. Examples of plastic materials include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), and polycarbonates (hereinafter And may be abbreviated as “PC”), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable. In a preferred embodiment, the support is a polyethylene terephthalate film.
支持体は、熱硬化性樹脂組成物層と接合する側の表面にマット処理、コロナ処理を施してあってもよい。また、支持体としては、熱硬化性樹脂組成物層と接合する側の表面に離型層を有する離型層付き支持体を使用してもよい。 In the support, the surface on the side to be bonded to the thermosetting resin composition layer may be subjected to a matting treatment and a corona treatment. Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface of the side joined to a thermosetting resin composition layer.
支持体の厚さは、特に限定されないが、5μm〜75μmの範囲が好ましく、10μm〜60μmの範囲がより好ましい。なお、支持体が離型層付き支持体である場合、離型層付き支持体全体の厚みが上記範囲であることが好ましい。 The thickness of the support is not particularly limited, but a range of 5 μm to 75 μm is preferable, and a range of 10 μm to 60 μm is more preferable. In addition, when a support body is a support body with a release layer, it is preferable that the thickness of the support body with a release layer is the said range.
接着フィルムは、例えば、有機溶剤に熱硬化性樹脂組成物を溶解した樹脂ワニスを調製し、この樹脂ワニスを、ダイコーターなどを用いて支持体上に塗布し、更に加熱、あるいは熱風吹きつけ等により有機溶剤を乾燥させて熱硬化性樹脂組成物層を形成させることにより製造することができる。 The adhesive film is prepared, for example, by preparing a resin varnish in which a thermosetting resin composition is dissolved in an organic solvent, applying the resin varnish on a support using a die coater or the like, and further heating or blowing with a hot air, etc. It can manufacture by drying an organic solvent by this, and forming a thermosetting resin composition layer.
有機溶剤としては、例えば、アセトン、メチルエチルケトン(以下「MEK」ともいう。)及びシクロヘキサノン等のケトン類、酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート及びカルビトールアセテート等の酢酸エステル類、セロソルブ及びブチルカルビトール等のカルビトール類、トルエン及びキシレン等の芳香族炭化水素類、ジメチルホルムアミド、ジメチルアセトアミド及びN−メチルピロリドン等のアミド系溶媒等を挙げることができる。有機溶剤は1種単独で用いてもよく、又は2種以上を併用してもよい。 Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (hereinafter also referred to as “MEK”) and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, acetates such as propylene glycol monomethyl ether acetate and carbitol acetate, Examples include carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. The organic solvents may be used alone or in combination of two or more.
乾燥条件は特に限定されないが、熱硬化性樹脂組成物層中の有機溶剤の含有量が10質量%以下、好ましくは5質量%以下となるように乾燥させる。樹脂ワニス中の有機溶剤の沸点によっても異なるが、例えば30質量%〜60質量%の有機溶剤を含む樹脂ワニスを用いる場合、50℃〜150℃で3〜10分乾燥させることにより、熱硬化性樹脂組成物層を形成することができる。 The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the thermosetting resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although different depending on the boiling point of the organic solvent in the resin varnish, for example, in the case of using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, thermosetting by drying at 50 ° C. to 150 ° C. for 3 to 10 minutes A resin composition layer can be formed.
接着フィルムにおいて、熱硬化性樹脂組成物層の支持体と接合していない面(即ち、支持体とは反対側の面)には、支持体に準じた保護フィルムをさらに積層することができる。保護フィルムの厚さは、特に限定されるものではないが、例えば、1μm〜40μmである。保護フィルムを積層することにより、熱硬化性樹脂組成物層の表面へのゴミ等の付着やキズを防止することができる。接着フィルムは、ロール状に巻きとって保存することが可能であり、本発明の粗化硬化体を製造する際には、保護フィルムを剥がすことによって使用可能となる。 In the adhesive film, a protective film according to the support can be further laminated on the surface of the thermosetting resin composition layer not bonded to the support (that is, the surface opposite to the support). Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to prevent adhesion of dust and the like to the surface of the thermosetting resin composition layer and scratches. The adhesive film can be wound and stored in a roll, and can be used by peeling off the protective film when producing the roughened cured product of the present invention.
本発明の粗化硬化体は、無機充填材含有量が50質量%以上である上記熱硬化性樹脂組成物の熱硬化体を粗化処理して得られる。例えば、本発明の粗化硬化体は、下記工程(A)及び(B)を含む方法により製造される。
(A)無機充填材含有量が50質量%以上である熱硬化性樹脂組成物を熱硬化させて熱硬化体を形成する工程
(B)熱硬化体を粗化処理して粗化硬化体を形成する工程
The roughening cured body of the present invention is obtained by roughening the thermosetting body of the above thermosetting resin composition having an inorganic filler content of 50% by mass or more. For example, the roughened cured product of the present invention is produced by a method including the following steps (A) and (B).
(A) Step of thermosetting the thermosetting resin composition having an inorganic filler content of 50% by mass or more to form a thermosetting body (B) roughening treatment of the thermosetting body to roughen the hardened body Forming process
工程(A)において使用する熱硬化性樹脂組成物の構成は上述のとおりである。表面のSi原子とO原子の割合が所望の範囲にある粗化硬化体を容易に実現できる観点から、無機充填材(好ましくはシリカ)、エポキシ樹脂、硬化剤及び熱可塑性樹脂を含む熱硬化性樹脂組成物を用いることが好ましく、無機充填材(好ましくはシリカ)、エポキシ樹脂、硬化剤、熱可塑性樹脂及び硬化促進剤を含む熱硬化性樹脂組成物を用いることがより好ましい。表面のSi原子とO原子の割合が所望の範囲にある粗化硬化体を容易に実現できる観点から、硬化剤としてはフェノール系硬化剤、ナフトール系硬化剤及び活性エステル系硬化剤からなる群から選択される1種以上を、熱可塑性樹脂としてはフェノキシ樹脂及びポリビニルアセタール樹脂からなる群から選択される1種以上を、硬化促進剤としてはアミン系硬化促進剤及びイミダゾール系硬化促進剤からなる群から選択される1種以上を、それぞれ用いることが好ましい。 The composition of the thermosetting resin composition used in the step (A) is as described above. A thermosetting resin containing an inorganic filler (preferably silica), an epoxy resin, a curing agent and a thermoplastic resin, from the viewpoint of easily realizing a roughened cured product in which the ratio of Si atoms to O atoms on the surface is in a desired range. It is preferable to use a resin composition, and it is more preferable to use a thermosetting resin composition containing an inorganic filler (preferably silica), an epoxy resin, a curing agent, a thermoplastic resin and a curing accelerator. From the viewpoint of easily achieving a roughened cured product in which the ratio of Si atoms to O atoms on the surface is in a desired range, a curing agent selected from the group consisting of phenolic curing agents, naphtholic curing agents and active ester curing agents A group consisting of at least one selected from the group consisting of phenoxy resin and polyvinyl acetal resin as a thermoplastic resin, and an amine-based curing accelerator and an imidazole-based curing accelerator as a curing accelerator It is preferable to use one or more selected from
工程(A)における熱硬化性樹脂組成物の熱硬化は、熱硬化性樹脂組成物を、所定の温度にて所定の時間加熱する条件(以下「ノンステップ条件」という。)にて実施してもよく、あるいは温度T1にて所定の時間加熱した後、温度T1よりも高い温度T2にて所定の時間加熱する条件(以下「ステップ条件」という。)で実施してもよい。なお、ステップ条件にて熱硬化性樹脂組成物を熱硬化させる場合、2段階の加熱(T1→T2)に限られず、3段階(T1→T2→T3)あるいはより多段階の加熱としてもよい。 The thermosetting of the thermosetting resin composition in the step (A) may be carried out under the conditions (hereinafter referred to as "non-step conditions") in which the thermosetting resin composition is heated at a predetermined temperature for a predetermined time. well, or after heating the predetermined time at a temperature T 1, it may be carried out under the conditions (hereinafter referred to as "step condition".) for heating a predetermined time at a higher temperature T 2 than the temperature T 1. When the thermosetting resin composition is thermally cured under the step conditions, it is not limited to two-stage heating (T 1 → T 2 ), but may be three stages (T 1 → T 2 → T 3 ) or more stages. It may be heating.
表面のSi原子とO原子の割合が所望の範囲にある粗化硬化体をより容易に実現できる観点から、ステップ条件にて熱硬化性樹脂組成物を熱硬化させることが好ましい。硬化剤として活性エステル系硬化剤を使用する場合には、ノンステップ条件やステップ条件にて熱硬化性樹脂組成物を熱硬化させる場合にも表面のSi原子とO原子の割合が所望の範囲にある粗化硬化体を容易に実現できる。 It is preferable that the thermosetting resin composition be thermally cured under the step conditions, from the viewpoint that a roughened cured product having a ratio of Si atoms to O atoms on the surface in a desired range can be easily realized. When an active ester-based curing agent is used as the curing agent, the ratio of Si atoms to O atoms on the surface is within the desired range even when the thermosetting resin composition is thermally cured under non-step conditions or step conditions. A roughened hardened body can be easily realized.
ノンステップ条件にて熱硬化性樹脂組成物を熱硬化させる場合、熱硬化性樹脂組成物の組成によっても異なるが、硬化温度は、好ましくは150℃〜240℃の範囲、より好ましくは150℃〜210℃の範囲、さらに好ましくは170℃〜190℃の範囲であり、硬化時間は、好ましくは5分間〜90分間の範囲、より好ましくは10分間〜75分間の範囲、さらに好ましくは15分間〜60分間の範囲である。室温から上記硬化温度までの昇温速度は特に制限されないが、好ましくは1.5℃/分〜30℃/分、より好ましくは2℃/分〜30℃/分である。 When thermosetting the thermosetting resin composition under non-step conditions, the curing temperature is preferably in the range of 150 ° C. to 240 ° C., more preferably 150 ° C. to 210, although it varies depending on the composition of the thermosetting resin composition. The curing time is preferably in the range of 5 minutes to 90 minutes, more preferably in the range of 10 minutes to 75 minutes, and still more preferably in the range of 15 minutes to 60 minutes. Range. The temperature raising rate from room temperature to the above curing temperature is not particularly limited, but is preferably 1.5 ° C./min to 30 ° C./min, more preferably 2 ° C./min to 30 ° C./min.
ステップ条件にて熱硬化性樹脂組成物を熱硬化させる場合、例えば、温度T1(但し50℃≦T1<150℃)にて10分間以上加熱した後、温度T2(但し150℃≦T2≦240℃)にて5分間以上加熱してよい。 In the case of thermosetting the thermosetting resin composition under the step conditions, for example, after heating for 10 minutes or more at a temperature T 1 (where 50 ° C. ≦ T 1 <150 ° C.), the temperature T 2 (where 150 ° C. ≦ T) The heating may be carried out at 2 ≦ 240 ° C. for 5 minutes or more.
ステップ条件において、温度T1は、熱硬化性樹脂組成物の組成にもよるが、好ましくは60℃≦T1≦130℃、より好ましくは70℃≦T1≦120℃、さらに好ましくは80℃≦T1≦110℃を満たす。 In the step conditions, the temperature T 1 depends on the composition of the thermosetting resin composition, but preferably 60 ° C. ≦ T 1 ≦ 130 ° C., more preferably 70 ° C. ≦ T 1 ≦ 120 ° C., further preferably 80 ° C. ≦ T 1 ≦ 110 ° C. is satisfied.
ステップ条件において、温度T1にて加熱する時間は、温度T1の値にもよるが、好ましくは10分間〜150分間、より好ましくは15分間〜120分間である。 In step condition, the time of heating at temperatures T 1 depends on the value of the temperatures T 1, preferably 10 minutes to 150 minutes, more preferably 15 minutes to 120 minutes.
ステップ条件において、温度T2は、熱硬化性樹脂組成物の組成にもよるが、好ましくは155℃≦T2≦230℃、より好ましくは160℃≦T2≦220℃、さらに好ましくは170℃≦T2≦210℃を満たす。 In step condition, temperature T 2, depending on the composition of the thermosetting resin composition, preferably from 155 ℃ ≦ T 2 ≦ 230 ℃ , more preferably 160 ℃ ≦ T 2 ≦ 220 ℃ , more preferably 170 ° C. ≦ T 2 ≦ 210 meet ° C..
なお、温度T1と温度T2は、好ましくは20℃≦T2−T1≦150℃、より好ましくは30℃≦T2−T1≦140℃、さらに好ましくは40℃≦T2−T1≦130℃、特に好ましくは50℃≦T2−T1≦120℃の関係を満たす。 The temperature T 1 and the temperature T 2 are preferably 20 ° C. ≦ T 2 −T 1 ≦ 150 ° C., more preferably 30 ° C. ≦ T 2 −T 1 ≦ 140 ° C., still more preferably 40 ° C. ≦ T 2 −T The relationship of 1 ≦ 130 ° C., particularly preferably 50 ° C. ≦ T 2 −T 1 ≦ 120 ° C. is satisfied.
ステップ条件において、温度T2にて加熱する時間は、温度T2の値にもよるが、好ましくは5分間〜100分間、より好ましくは10分間〜80分間、さらに好ましくは10分間〜50分間である。 In step condition, the time of heating at a temperature T 2 depends on the value of temperature T 2, preferably 5 minutes to 100 minutes, more preferably 10 minutes to 80 minutes, more preferably 50 minutes to 10 minutes is there.
ステップ条件において、室温から温度T1までの昇温速度は特に制限されないが、好ましくは1.5℃/分〜30℃/分、より好ましくは2℃/分〜30℃/分である。また、温度T1から温度T2への昇温速度は、好ましくは1.5℃/分〜30℃/分、より好ましくは2℃/分〜30℃/分、さらに好ましくは4℃/分〜20℃/分、さらにより好ましくは4℃/分〜10℃/分である。 In the step conditions, the heating rate from room temperature to the temperature T 1 is not particularly limited, but is preferably 1.5 ° C./min to 30 ° C./min, more preferably 2 ° C./min to 30 ° C./min. Further, heating rate from temperature T 1 of the temperature T 2 is preferably 1.5 ° C. / min to 30 ° C. / min, more preferably 2 ° C. / min to 30 ° C. / min, more preferably 4 ° C. / min -20 ° C / min, even more preferably 4 ° C / min to 10 ° C / min.
熱硬化性樹脂組成物の熱硬化は、常圧下で実施しても減圧下で実施してもよいが、表面のSi原子とO原子の割合が所望の範囲にある粗化硬化体を容易に実現できる観点から、好ましくは0.075mmHg〜3751mmHg(0.1hPa〜5000hPa)の範囲、より好ましくは1mmHg〜1875mmHg(1.3hPa〜2500hPa)の範囲の空気圧にて実施することが好ましい。 The thermosetting of the thermosetting resin composition may be carried out under normal pressure or under reduced pressure, but a roughened cured body having a ratio of Si atoms to O atoms in the surface in a desired range is easily From the viewpoint of realization, it is preferable to carry out at an air pressure in the range of preferably 0.075 mmHg to 3751 mmHg (0.1 hPa to 5000 hPa), more preferably 1 mmHg to 1875 mmHg (1.3 hPa to 2500 hPa).
こうして形成される熱硬化体は、上述のとおり、JIS K5600−5−4(ISO 15184)に準拠して測定された、表面の引っかき硬度が高く、また、X線光電子分光法により測定した、表面のSi量が低い傾向にある。斯かる熱硬化体は、後述する工程(B)の粗化処理において、表面が適度に粗化されるため、表面粗度の過度の上昇を抑えることができる。また、粗化処理後に表面のSi原子とO原子の割合が所望の範囲となることから、表面が低粗度であっても導体層に対して高い剥離強度を呈する粗化硬化体を実現することができる。 The thermosetting body thus formed has a high surface scratch hardness measured according to JIS K 5600-5-4 (ISO 15184) as described above, and a surface measured by X-ray photoelectron spectroscopy. The amount of Si tends to be low. The surface of such a thermally cured product is appropriately roughened in the roughening treatment in step (B) described later, so that an excessive increase in surface roughness can be suppressed. In addition, since the ratio of Si atoms and O atoms on the surface is in the desired range after the roughening treatment, a roughened hardened body exhibiting high peel strength to the conductor layer is realized even if the surface has low roughness. be able to.
工程(B)における粗化処理の手順、条件は特に限定されず、プリント配線板の絶縁層を形成するに際して通常使用される公知の手順、条件を採用することができる。 The procedure and conditions of the roughening treatment in the step (B) are not particularly limited, and known procedures and conditions generally used in forming an insulating layer of a printed wiring board can be adopted.
例えば、膨潤液による膨潤処理、酸化剤による粗化処理、中和液による中和処理をこの順に実施して硬化体表面を粗化処理することができる。膨潤液としては特に限定されないが、アルカリ溶液、界面活性剤溶液等が挙げられ、好ましくはアルカリ溶液であり、該アルカリ溶液としては、水酸化ナトリウム溶液、水酸化カリウム溶液がより好ましい。市販されている膨潤液としては、例えば、アトテックジャパン(株)製のスウェリング・ディップ・セキュリガンスP、スウェリング・ディップ・セキュリガンスSBU等が挙げられる。膨潤液による膨潤処理は、特に限定されないが、例えば、30〜90℃の膨潤液に硬化体を1分間〜20分間浸漬することにより行うことができる。硬化体の樹脂の膨潤を適度なレベルに抑える観点から、40〜80℃の膨潤液に硬化体を5秒間〜15分間浸漬させることが好ましい。酸化剤としては、特に限定されないが、例えば、水酸化ナトリウムの水溶液に過マンガン酸カリウムや過マンガン酸ナトリウムを溶解したアルカリ性過マンガン酸溶液が挙げられる。アルカリ性過マンガン酸溶液等の酸化剤による粗化処理は、60℃〜80℃に加熱した酸化剤溶液に硬化体を10分間〜30分間浸漬させて行うことが好ましい。また、アルカリ性過マンガン酸溶液における過マンガン酸塩の濃度は5質量%〜10質量%が好ましい。市販されている酸化剤としては、例えば、アトテックジャパン(株)製のコンセントレート・コンパクトP、ドージングソリューション・セキュリガンスP等のアルカリ性過マンガン酸溶液が挙げられる。また、中和液としては、酸性の水溶液が好ましく、市販品としては、例えば、アトテックジャパン(株)製のリダクションショリューシン・セキュリガントPが挙げられる。中和液による処理は、酸化剤溶液による粗化処理がなされた処理面を30〜80℃の中和液に5分間〜30分間浸漬させることにより行うことができる。作業性等の点から、酸化剤溶液による粗化処理がなされた対象物を、40〜70℃の中和液に5分間〜20分間浸漬する方法が好ましい。 For example, the surface of the cured product can be roughened by performing a swelling treatment with a swelling solution, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution in this order. The swelling liquid is not particularly limited, and examples thereof include an alkaline solution, a surfactant solution and the like, preferably an alkaline solution, and as the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. As a swelling liquid marketed, Swelling dip security g P made from Atotech Japan Co., Ltd., swelling dip security G SBU etc. are mentioned, for example. Although the swelling process by a swelling liquid is not specifically limited, For example, it can carry out by immersing hardened | cured material in a 30-90 degreeC swelling liquid for 1 minute-20 minutes. From the viewpoint of suppressing the swelling of the resin of the cured product to an appropriate level, it is preferable to immerse the cured product in a swelling liquid at 40 to 80 ° C. for 5 seconds to 15 minutes. Although it does not specifically limit as an oxidizing agent, For example, the alkaline permanganic acid solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the cured product in the oxidizing agent solution heated to 60 ° C. to 80 ° C. for 10 minutes to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrate Compact P and Dosing Solutions Securigans P manufactured by Atotech Japan Co., Ltd. In addition, as the neutralization solution, an acidic aqueous solution is preferable, and as a commercial product, for example, Reduction Sholeucine Securigant P manufactured by Atotech Japan Co., Ltd. can be mentioned. The treatment with the neutralization solution can be carried out by immersing the treated surface roughened with the oxidizing agent solution in the neutralization solution at 30 to 80 ° C. for 5 minutes to 30 minutes. From the viewpoint of workability and the like, it is preferable to immerse the object roughened with the oxidizing agent solution in a neutralization solution at 40 to 70 ° C. for 5 minutes to 20 minutes.
こうして得られた本発明の粗化硬化体は、無機充填材含有量が高いという特性を保持しつつ、表面の粗度が低く且つ導体層に対して優れた剥離強度を呈することから、プリント配線板の微細配線化に著しく寄与するものである。 The roughened cured product of the present invention thus obtained has a low surface roughness and exhibits excellent peel strength with respect to the conductor layer while maintaining the characteristic that the content of the inorganic filler is high. It significantly contributes to the miniaturization of the board.
[積層体]
本発明の積層体は、本発明の粗化硬化体と、該粗化硬化体の表面に形成された導体層とを備える。
[Laminate]
The laminate of the present invention comprises the roughened cured product of the present invention and a conductor layer formed on the surface of the roughened cured product.
導体層は金属層からなり、導体層に使用する金属は特に限定されないが、好適な一実施形態では、導体層は、金、白金、銀、銅、アルミニウム、コバルト、クロム、亜鉛、ニッケル、チタン、タングステン、鉄、スズ及びインジウムからなる群から選択される1種以上の金属を含む。導体層は、単金属層であっても合金層であってもよく、合金層としては、例えば、上記の群から選択される2種以上の金属の合金(例えば、ニッケル・クロム合金、銅・ニッケル合金及び銅・チタン合金)から形成された層が挙げられる。中でも、金属層形成の汎用性、コスト、エッチングによる除去の容易性等の観点から、クロム、ニッケル、チタン、アルミニウム、亜鉛、金、銀若しくは銅の単金属層、又はニッケル・クロム合金、銅・ニッケル合金、銅・チタン合金の合金層が好ましく、クロム、ニッケル、チタン、アルミニウム、亜鉛、金、銀若しくは銅の単金属層、又はニッケル・クロム合金の合金層がより好ましく、銅の単金属層が更に好ましい。 The conductor layer is composed of a metal layer, and the metal used for the conductor layer is not particularly limited. However, in a preferred embodiment, the conductor layer is made of gold, platinum, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium And at least one metal selected from the group consisting of tungsten, iron, tin and indium. The conductor layer may be a single metal layer or an alloy layer, and as the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper, And layers formed of nickel alloy and copper-titanium alloy). Among them, chromium, nickel, titanium, aluminum, zinc, gold, gold, silver or copper single metal layer, nickel-chromium alloy, copper, from the viewpoint of versatility of metal layer formation, cost, ease of removal by etching, etc. An alloy layer of nickel alloy, copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, silver or copper, or an alloy layer of nickel-chromium alloy is more preferable, a single metal layer of copper Is more preferred.
導体層は、単層構造であっても、異なる種類の金属若しくは合金からなる単金属層又は合金層が2層以上積層した複層構造であってもよい。導体層が複層構造である場合、粗化硬化体と接する層は、クロム、亜鉛若しくはチタンの単金属層、又はニッケル・クロム合金の合金層であることが好ましい。 The conductor layer may have a single-layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer in contact with the roughened hardened body is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of a nickel-chromium alloy.
導体層の厚さは、プリント配線板の微細配線化の観点から、40μm以下が好ましく、1〜35μmがより好ましく、3〜20μmが更に好ましい。金属層が複層構造である場合も、金属層全体の厚みは上記範囲であることが好ましい。 The thickness of the conductor layer is preferably 40 μm or less, more preferably 1 to 35 μm, and still more preferably 3 to 20 μm from the viewpoint of microwiring of the printed wiring board. Even when the metal layer has a multilayer structure, the thickness of the entire metal layer is preferably in the above range.
導体層は、乾式メッキ又は湿式メッキにより形成することができる。乾式メッキとしては、例えば、蒸着、スパッタリング、イオンプレーティング等の公知の方法が挙げられる。湿式メッキの場合は、例えば、無電解メッキと電解メッキとを組み合わせて金属層を形成する。あるいは、金属層(導体層)とは逆パターンのメッキレジストを形成し、無電解メッキのみで金属層を形成することもできる。配線パターン形成の方法としては、例えば、当業者に公知のサブトラクティブ法、セミアディティブ法などを用いることができる。 The conductor layer can be formed by dry plating or wet plating. Examples of dry plating include known methods such as vapor deposition, sputtering and ion plating. In the case of wet plating, for example, electroless plating and electrolytic plating are combined to form a metal layer. Alternatively, a plating resist having a pattern reverse to that of the metal layer (conductor layer) may be formed, and the metal layer may be formed only by electroless plating. As a method of forming a wiring pattern, for example, a subtractive method, a semi-additive method or the like known to those skilled in the art can be used.
導体層の厚さは、プリント配線板の微細配線化の観点から、40μm以下が好ましく、1〜35μmがより好ましく、3〜20μmが更に好ましい。導体層が複層構造である場合も、導体層全体の厚みは上記範囲であることが好ましい。 The thickness of the conductor layer is preferably 40 μm or less, more preferably 1 to 35 μm, and still more preferably 3 to 20 μm from the viewpoint of microwiring of the printed wiring board. Even when the conductor layer has a multilayer structure, the thickness of the entire conductor layer is preferably in the above range.
本発明の積層体において、粗化硬化体と導体層との剥離強度は、好ましくは0.3kgf/cm以上、より好ましくは0.4kgf/cm以上、さらに好ましくは0.5kgf/cm以上、さらにより好ましくは0.55kgf/cm以上、特に好ましくは0.6kgf/cm以上である。一方、剥離強度の上限は特に制限されないが、1.2kgf/cm以下、0.9kgf/cm以下などとなる。
本発明の積層体は、粗化硬化体の表面の算術平均粗さRaが350nm未満と小さいにもかかわらず、このように高い剥離強度を呈することから、プリント配線板の微細配線化に著しく寄与するものである。
なお本発明において、粗化硬化体と導体層との剥離強度とは、導体層を粗化硬化体に対して垂直方向(90度方向)に引き剥がしたときの剥離強度(90度ピール強度)をいい、導体層を粗化硬化体に対して垂直方向(90度方向)に引き剥がしたときの剥離強度を引っ張り試験機で測定することにより求めることができる。引っ張り試験機としては、例えば、(株)TSE製の「AC−50C−SL」等が挙げられる。
In the laminate of the present invention, the peel strength between the roughened cured product and the conductor layer is preferably 0.3 kgf / cm or more, more preferably 0.4 kgf / cm or more, still more preferably 0.5 kgf / cm or more More preferably, it is 0.55 kgf / cm or more, particularly preferably 0.6 kgf / cm or more. On the other hand, the upper limit of the peel strength is not particularly limited, but is 1.2 kgf / cm or less, 0.9 kgf / cm or less, or the like.
Although the laminate of the present invention exhibits such high peel strength despite the fact that the arithmetic mean roughness Ra of the surface of the roughened cured body is as small as less than 350 nm, it significantly contributes to the fine wiring of the printed wiring board It is
In the present invention, the peel strength between the roughened cured product and the conductor layer is the peel strength (90 degree peel strength) when the conductive layer is peeled off in the direction perpendicular to the roughened cured product (90 degrees direction). It can be determined by measuring the peel strength when the conductor layer is peeled off in the direction perpendicular to the roughening cured body (90 degrees direction) with a tensile tester. As a tension tester, "AC-50C-SL" made from TSE Co., Ltd. etc. are mentioned, for example.
[プリント配線板]
本発明のプリント配線板は、本発明の硬化体により絶縁層が形成されることを特徴とする。
[Printed wiring board]
The printed wiring board of the present invention is characterized in that an insulating layer is formed of the cured product of the present invention.
一実施形態において、本発明のプリント配線板は、上述の接着フィルムを用いて製造することができる。斯かる実施形態においては、接着フィルムの熱硬化性樹脂組成物層が回路基板と接合するようにラミネート処理した後、上述の「工程(A)」及び「工程(B)」を実施して本発明の粗化硬化体を回路基板上に形成することができる。接着シートが保護フィルムを有する場合、保護フィルムを除去した後に製造に供することができる。なお、支持体の剥離は、ラミネート処理と工程(A)の間に実施してもよく、工程(A)の後に実施してもよいが、表面のSi原子とO原子の割合が所望の範囲にある粗化硬化体を容易に実現する観点から、ラミネート処理と工程(A)の間に実施することが好ましい。 In one embodiment, the printed wiring board of the present invention can be manufactured using the above-mentioned adhesive film. In such an embodiment, after the laminating process is performed so that the thermosetting resin composition layer of the adhesive film is bonded to the circuit board, the above-described "step (A)" and "step (B)" are performed to carry out the present process. The roughened cured product of the invention can be formed on a circuit board. When the adhesive sheet has a protective film, it can be subjected to production after removing the protective film. In addition, although peeling of a support body may be implemented between a lamination process and a process (A) and may be implemented after a process (A), the ratio of Si atom of a surface and O atom is a desired range. It is preferable to carry out between a lamination process and a process (A) from a viewpoint of implement | achieving easily the roughening hardening body which exists in (4).
ラミネート処理の条件は特に限定されず、接着フィルムを用いてプリント配線板の絶縁層を形成するにあたり使用される公知の条件を採用することができる。例えば、加熱されたSUS鏡板等の金属板を接着フィルムの支持体側からプレスすることにより行うことができる。この場合、金属板を直接プレスするのではなく、回路基板の回路凹凸に接着フィルムが十分に追随するよう、耐熱ゴム等の弾性材を介してプレスを行うのが好ましい。プレス温度は、好ましくは70℃〜140℃の範囲であり、プレス圧力は好ましくは1kgf/cm2〜11kgf/cm2(0.098MPa〜1.079MPa)の範囲で行われ、プレス時間は好ましくは5秒間〜3分間の範囲である。また、ラミネート処理は、好ましくは20mmHg(26.7hPa)以下の減圧下で実施する。ラミネート処理は、市販されている真空ラミネーターを用いて実施することができる。市販されている真空ラミネーターとしては、例えば、(株)名機製作所製の真空加圧式ラミネーター、ニチゴー・モートン(株)製のバキュームアップリケーター等が挙げられる。 The conditions for the lamination process are not particularly limited, and any known conditions used to form an insulating layer of a printed wiring board using an adhesive film can be adopted. For example, it can carry out by pressing metal plates, such as a heated SUS end plate, from the support body side of adhesive film. In this case, it is preferable not to press the metal plate directly but to perform pressing via an elastic material such as heat-resistant rubber so that the adhesive film sufficiently follows the circuit irregularities of the circuit board. The press temperature is preferably in the range of 70 ° C. to 140 ° C., the press pressure is preferably in the range of 1 kgf / cm 2 to 11 kgf / cm 2 (0.098 MPa to 1.079 MPa), and the press time is preferably It is in the range of 5 seconds to 3 minutes. The lamination process is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less. The lamination process can be carried out using a commercially available vacuum laminator. As a vacuum laminator marketed, a vacuum pressure type laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nichigo Morton Co., Ltd., etc. may be mentioned.
なお、本発明において、「回路基板」とは、主として、ガラスエポキシ基板、金属基板、ポリエステル基板、ポリイミド基板、BTレジン基板、熱硬化型ポリフェニレンエーテル基板等の基板の片面又は両面にパターン加工された導体層(回路)が形成されたものをいう。またプリント配線板を製造する際に、さらに絶縁層及び/又は導体層が形成されるべき中間製造物の内層回路基板も本発明でいう「回路基板」に含まれる。 In the present invention, the "circuit board" is mainly patterned on one side or both sides of a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, or a thermosetting polyphenylene ether substrate. It refers to one in which a conductor layer (circuit) is formed. Further, when manufacturing a printed wiring board, an inner layer circuit board of an intermediate product on which an insulating layer and / or a conductor layer is to be formed is also included in the "circuit board" in the present invention.
他の実施形態において、本発明のプリント配線板は、上述の樹脂ワニスを用いて製造することができる。斯かる実施形態においては、樹脂ワニスをダイコーター等により回路基板上に均一に塗布し、加熱、乾燥させることにより回路基板上に熱硬化性樹脂組成物層を形成した後、上述の「工程(A)」及び「工程(B)」を実施して本発明の粗化硬化体を回路基板上に形成することができる。樹脂ワニスに使用する有機溶剤並びに加熱、乾燥の条件は、接着フィルムの製造について説明したものと同様とし得る。 In another embodiment, the printed wiring board of the present invention can be manufactured using the above-mentioned resin varnish. In such an embodiment, a resin varnish is uniformly applied on a circuit board by a die coater or the like, heated and dried to form a thermosetting resin composition layer on the circuit board, and then the above-mentioned “step ( "A)" and "Step (B)" can be carried out to form the roughened cured product of the present invention on a circuit board. The organic solvent used for the resin varnish and the heating and drying conditions may be the same as those described for the production of the adhesive film.
次いで、回路基板上に形成された粗化硬化体の表面に導体層を形成する。なお、プリント配線板の製造においては、絶縁層にビアを形成する工程、ビア内部の樹脂残渣(スミア)を除去する工程等をさらに含んでもよい。これらの工程は、当業者に公知である、プリント配線板の製造に用いられている各種方法に従って行うことができる。 Next, a conductor layer is formed on the surface of the roughening cured body formed on the circuit board. The manufacturing of the printed wiring board may further include a step of forming a via in the insulating layer, a step of removing a resin residue (smear) inside the via, and the like. These steps can be performed according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards.
本発明のプリント配線板は、クラックや回路歪みの発生なしに回路の微細配線化を有利に実現するものである。 The printed wiring board of the present invention advantageously realizes the fine wiring of the circuit without the occurrence of the crack and the circuit distortion.
[半導体装置]
上記のプリント配線板を用いて、半導体装置を製造することができる。
[Semiconductor device]
A semiconductor device can be manufactured using the above printed wiring board.
かかる半導体装置としては、電気製品(例えば、コンピューター、携帯電話、デジタルカメラ及びテレビ等)及び乗物(例えば、自動二輪車、自動車、電車、船舶及び航空機等)等に供される各種半導体装置が挙げられる。 Examples of such semiconductor devices include various semiconductor devices provided for electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft etc.), etc. .
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、以下の記載において、「部」及び「%」は、別途明示のない限り、それぞれ「質量部」及び「質量%」を意味する。 EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In the following description, “parts” and “%” mean “parts by mass” and “% by mass”, respectively, unless otherwise specified.
まず各種測定方法・評価方法について説明する。 First, various measurement methods and evaluation methods will be described.
〔測定・評価用サンプルの調製〕
(1)回路基板の下地処理
内層回路の形成されたガラス布基材エポキシ樹脂両面銅張積層板(銅箔厚さ18μm、基板厚さ0.3mm、松下電工(株)製「R5715ES」)の両面を、メック(株)製「CZ8100」に浸漬し1μmエッチングして銅表面の粗化処理を行った。
[Preparation of sample for measurement and evaluation]
(1) Substrate treatment of circuit board A glass cloth-based epoxy resin double-sided copper-clad laminated board (copper foil thickness 18 μm, substrate thickness 0.3 mm, "R5715 ES" manufactured by Matsushita Electric Works Co., Ltd.) on which inner layer circuits are formed Both surfaces were immersed in “CZ8100” manufactured by MEC Co., Ltd., and etched for 1 μm to roughen the copper surface.
(2)接着フィルムのラミネート処理
実施例及び比較例で作製した接着フィルムを、バッチ式真空加圧ラミネーター(名機(株)製「MVLP-500」)を用いて、熱硬化性樹脂組成物層が内層回路基板と接合するように、内層回路基板の両面にラミネート処理した。ラミネート処理は、30秒間減圧して気圧を13hPa以下とした後、100℃、圧力0.74MPaで30秒間プレスすることにより行った。
(2) Lamination treatment of adhesive film A thermosetting resin composition layer was produced using the adhesive films prepared in the examples and comparative examples as a batch type vacuum pressure laminator ("MVLP-500" manufactured by Meishin Co., Ltd.). The laminate was laminated on both sides of the inner layer circuit board so as to bond with the inner layer circuit board. The lamination treatment was performed by reducing the pressure for 30 seconds to make the pressure 13 hPa or less, and pressing for 30 seconds at 100 ° C. and a pressure of 0.74 MPa.
(3)熱硬化性樹脂組成物層の熱硬化
熱硬化性樹脂組成物層のラミネート処理後、熱硬化性樹脂組成物層を熱硬化させて、内層回路基板の両面上に熱硬化体を形成した。その際、実施例1〜4及び比較例1、2に関しては、支持体であるPETフィルムを剥離した後に熱硬化性樹脂組成物層を熱硬化させた。実施例5に関しては、支持体であるPETフィルムが付着した状態で熱硬化性樹脂組成物層を熱硬化させた。
熱硬化性樹脂組成物層の熱硬化は、実施例1、2、4及び5に関しては下記ステップ条件にて、実施例3及び比較例1、2に関しては下記ノンステップ条件にて、それぞれ実施した。
ステップ条件:室温(20℃)から10℃/分にて昇温し100℃で30分間保持した後、10℃/分にて昇温し180℃で30分間保持
ノンステップ条件:室温(20℃)から10℃/分にて昇温し180℃で30分間保持
(3) Thermosetting of the thermosetting resin composition layer After lamination processing of the thermosetting resin composition layer, the thermosetting resin composition layer is thermosetted to form thermosetting bodies on both sides of the inner layer circuit board did. At that time, with respect to Examples 1 to 4 and Comparative Examples 1 and 2, the thermosetting resin composition layer was thermally cured after the PET film as a support was peeled off. With respect to Example 5, the thermosetting resin composition layer was thermally cured in the state where the PET film as the support was attached.
The thermosetting of the thermosetting resin composition layer was carried out under the following step conditions for Examples 1, 2, 4 and 5, and under the following non-step conditions for Example 3 and Comparative Examples 1 and 2.
Step conditions: Temperature rising from room temperature (20 ° C.) at 10 ° C./min and holding at 100 ° C. for 30 minutes, temperature rising at 10 ° C./min, holding at 180 ° C. for 30 minutes Non-step conditions: Room temperature (20 ° C.) Temperature from 10 ° C / min to 30 min at 180 ° C
得られた熱硬化体について、引っかき硬度、表面Si量及び表面O量を測定すると共に、単位表面積当たりのエッチング量を評価した。 About the obtained thermosetting body, while measuring scratch hardness, surface Si amount, and surface O amount, the etching amount per unit surface area was evaluated.
(4)粗化処理
両面上に熱硬化体が形成された内層回路基板を、膨潤液(アトテックジャパン(株)「スエリングディップ・セキュリガントP」、ジエチレングリコールモノブチルエーテル含有の水酸化ナトリウム水溶液)に60℃で5分間浸漬し、次いで酸化剤(アトテックジャパン(株)「コンセントレート・コンパクトP」、過マンガン酸カリウム濃度約6質量%、水酸化ナトリウム濃度約4質量%の水溶液)に80℃で20分間浸漬した。その後、1分間水洗した後、中和液(アトテックジャパン(株)「リダクションショリューシン・セキュリガントP」、硫酸ヒドロキシルアミン水溶液)に40℃で5分間浸漬し、内層回路基板の両面上に粗化硬化体を形成した。
得られた粗化硬化体について、表面のSi量、表面O量、表面の算術平均粗さRaを測定した。
(4) Coarsening treatment The inner layer circuit board having a thermally cured product formed on both sides is treated with a swelling solution (Atotech Japan Co., Ltd. "Swelling Dip Security G", sodium hydroxide aqueous solution containing diethylene glycol monobutyl ether). Soak at 80 ° C for 20 minutes in an oxidizing agent (Atotech Japan Ltd. "Concentrate Compact P", an aqueous solution of potassium permanganate concentration of about 6% by mass, sodium hydroxide concentration of about 4% by mass). Soak for a minute. Then, after washing with water for 1 minute, the substrate is immersed in a neutralization solution (Atotech Japan Co., Ltd. "Reduction choleucine secligant P", an aqueous solution of hydroxylamine sulfate) for 5 minutes at 40 ° C to roughen the inner layer circuit board on both sides. A hardened body was formed.
The amount of Si on the surface, the amount of O on the surface, and the arithmetic mean roughness Ra of the surface were measured for the obtained roughened cured product.
(5)導体層の形成
セミアディティブ法に従って、粗化硬化体の表面に導体層を形成した。
すなわち、両面上に粗化硬化体が形成された内層回路基板を、パラジウム化合物(Pd)を含む無電解銅めっき液に浸漬し、粗化硬化体表面にめっきシード層を形成した。その後、150℃にて30分間加熱してアニール処理を行った後に、めっきシード層上にエッチングレジストを形成し、エッチングによりめっきシード層をパターン形成した。次いで、硫酸銅電解めっきを行い、30±5μmの厚さの銅層を形成した後、180℃にて60分間アニール処理し、粗化硬化体の表面に導体層を形成した。
(5) Formation of conductor layer A conductor layer was formed on the surface of the roughened cured body according to the semi-additive method.
That is, the inner layer circuit board having the roughened cured product formed on both surfaces was immersed in an electroless copper plating solution containing a palladium compound (Pd) to form a plating seed layer on the surface of the roughened cured product. Then, after performing an annealing process by heating at 150 ° C. for 30 minutes, an etching resist was formed on the plating seed layer, and the plating seed layer was patterned by etching. Then, copper sulfate electrolytic plating was performed to form a copper layer having a thickness of 30 ± 5 μm, and then annealing treatment was performed at 180 ° C. for 60 minutes to form a conductor layer on the surface of the roughened cured body.
<引っかき硬度の測定>
熱硬化体の表面の引っかき硬度は、JIS K5600−5−4に準拠して測定した。測定に使用した鉛筆は三菱鉛筆(株)製「uni」であった。
<Measurement of scratch hardness>
The scratch hardness of the surface of the thermosetting body was measured in accordance with JIS K5600-5-4. The pencil used for the measurement was "uni" manufactured by Mitsubishi Pencil Co., Ltd.
<熱硬化体の単位表面積当たりのエッチング量の評価>
熱硬化体の単位表面積当たりのエッチング量は、下記に従って評価した。
すなわち、実施例及び比較例で調製した樹脂ワニスを、アルキド樹脂系離型層付きPETフィルム((株)リンテック製「AL-5」が塗布されたPETフィルム、以下「離型層付きPET」という)上に、ダイコータにて均一に塗布し、75℃で3分間乾燥させて、厚さ10μmの熱硬化性樹脂組成物層を形成した。次いで、実施例1、2、4及び5に関しては上記「ステップ条件」にて、また実施例3及び比較例1、2に関しては上記「ノンステップ条件」にて、それぞれ加熱して熱硬化体を得た。その後、離型層付きPETを剥離して、130℃で15分間乾燥させた。得られた試料の乾燥直後の質量(初期の質量(X1))を測定した。次いで、上記〔測定・評価用サンプルの調製〕欄の「(4)粗化処理」と同一条件にて熱硬化体の表面を粗化処理した。粗化処理の後、水洗し、130℃で15分間乾燥させた。得られた粗化試料の乾燥直後の質量(粗化処理後の質量(X2))を測定した。そして、下記式により、各熱硬化体の単位表面積当たりのエッチング量を求めた。
<Evaluation of the amount of etching per unit surface area of a thermosetting body>
The etching amount per unit surface area of the thermosetting body was evaluated according to the following.
That is, the resin varnish prepared in Examples and Comparative Examples is referred to as a PET film coated with an alkyd resin-based release layer (PET film coated with “AL-5” manufactured by Lintec Co., Ltd., hereinafter referred to as “PET with release layer” The solution was uniformly applied by a die coater and dried at 75 ° C. for 3 minutes to form a thermosetting resin composition layer having a thickness of 10 μm. Then, heat is obtained by heating under the above-mentioned "step conditions" for Examples 1, 2, 4 and 5 and under the above "non-step conditions" for Example 3 and Comparative Examples 1 and 2. The Thereafter, the PET with release layer was peeled off and dried at 130 ° C. for 15 minutes. The mass immediately after drying (initial mass (X1)) of the obtained sample was measured. Next, the surface of the thermosetting body was roughened under the same conditions as “(4) Roughening treatment” in the above “Preparation of sample for measurement and evaluation” column. After the roughening treatment, it was washed with water and dried at 130 ° C. for 15 minutes. The mass (mass after roughening treatment (X2)) immediately after drying of the obtained roughened sample was measured. And the etching amount per unit surface area of each thermosetting object was calculated | required by the following formula.
単位表面積当たりのエッチング量(g/m2)=(X1−X2)/硬化物の表面積 Amount of etching per unit surface area (g / m 2 ) = (X 1 -X 2) / surface area of cured product
<表面Si量及び表面O量の測定>
熱硬化体の表面Si量及び表面O量は、下記の測定装置および測定条件を用いて、X線光電子分光法により測定した。粗化硬化体の表面Si量及び表面O量も同様にして測定した。
〔測定装置〕
装置型式:QUANTERA SXM(アルバックファイ社製 全自動走査型X線光電子分光分析装置)
到達真空度:7.0×10−10Torr
X線源:単色化 Al Kα(1486.6eV)
分光器:静電同心半球型分析器
検出器:多チャンネル式(32 Multi−Channel Detector)
中和銃設定 電子:1.0 V (20μA)、イオン:10.0V(7mA)
〔測定条件〕
[サーベイスペクトル(ワイドスキャン)]
X線ビーム径:100μmΦ(HPモード、100.6W、20kV)
測定領域:1400μm×100μm
信号の取り込み角:45.0°
パスエネルギー:280.0eV
<Measurement of surface Si content and surface O content>
The amount of surface Si and the amount of surface O of the thermosetting body were measured by X-ray photoelectron spectroscopy using the following measuring apparatus and measuring conditions. The surface Si amount and the surface O amount of the roughened hardened body were also measured in the same manner.
〔measuring device〕
Device type: QUANTERA SXM (Full-vacuated full automatic scanning X-ray photoelectron spectrometer)
Ultimate vacuum: 7.0 × 10 -10 Torr
X-ray source: monochromized Al K α (1486.6 eV)
Spectrometer: Electrostatic concentric hemispherical analyzer Detector: Multi-channel (32 Multi-Channel Detector)
Neutralization gun setting Electron: 1.0 V (20 μA), ion: 10.0 V (7 mA)
〔Measurement condition〕
[Survey spectrum (wide scan)]
X-ray beam diameter: 100 μm HP (HP mode, 100.6 W, 20 kV)
Measurement area: 1400 μm × 100 μm
Signal capture angle: 45.0 °
Path energy: 280.0 eV
<算術平均粗さRaの測定>
粗化硬化体の表面の算術平均粗さRaは、非接触型表面粗さ計(ビーコインスツルメンツ社製「WYKO NT3300」)を用いて、VSIコンタクトモード、50倍レンズにより測定範囲を121μm×92μmとして得られる数値により求めた。各粗化硬化体について、10点の平均値を求めた。
<Measurement of Arithmetic Average Roughness Ra>
Arithmetic mean roughness Ra of the surface of the roughened hardened body is measured in a 121 μm × 92 μm measurement range by a VSI contact mode, 50 × lens using a non-contact surface roughness meter (“WYKO NT3300” manufactured by B-Coin Instruments Co., Ltd.) It calculated | required by the obtained numerical value. The average value of 10 points was determined for each roughened cured product.
<剥離強度の測定>
粗化硬化体と導体層との剥離強度は、下記に従って測定した。
すなわち、得られた積層体の導体層に、幅10mm、長さ100mmの部分の切込みをいれ、この一端を剥がしてつかみ具で掴み、室温中にて、50mm/分の速度で垂直方向に35mmを引き剥がした時の荷重(kgf/cm)を測定し、剥離強度を求めた。測定には、引っ張り試験機((株)TSE製、「AC−50C−SL」)を使用した。
<Measurement of peel strength>
The peel strength between the roughened cured product and the conductor layer was measured according to the following.
That is, insert a cut of 10 mm in width and 100 mm in length into the conductor layer of the obtained laminate, peel off one end and grip with a clamp, and vertically 35 mm at a speed of 50 mm / min in room temperature. The load (kgf / cm) when peeling off was measured to determine the peel strength. For measurement, a tensile tester (manufactured by TSE, “AC-50C-SL”) was used.
〔作製例1〕
(1)樹脂ワニス1の調製
液状ビスフェノールA型エポキシ樹脂(エポキシ当量180、三菱化学(株)製「jER828EL」)10部、ビフェニル型エポキシ樹脂(エポキシ当量269、日本化薬(株)製「NC3000L」)20部、4官能ナフタレン型エポキシ樹脂(エポキシ当量163、DIC(株)製「HP4700」)6部、及びフェノキシ樹脂(三菱化学(株)製「YL7553BH30」、固形分30質量%のMEKとシクロヘキサノンの1:1溶液、重量平均分子量35000)10部を、MEK5部、シクロヘキサノン5部及びソルベントナフサ15部の混合溶媒に撹拌しながら加熱溶解させた。室温まで冷却した後、そこへ、トリアジン含有フェノールノボラック系硬化剤(水酸基当量125、DIC(株)製「LA7054」、固形分60質量%のMEK溶液)15部、ナフトール系硬化剤(水酸基当量215、東都化成(株)製「SN−485」、固形分60%のMEK溶液)15部、アミン系硬化促進剤(4−ジメチルアミノピリジン(DMAP)、固形分5質量%のMEK溶液)1部、イミダゾール系硬化促進剤(1−ベンジル−2−フェニルイミダゾール、四国化成工業(株)製「1B2PZ」、固形分5質量%のMEK溶液)0.3部、難燃剤(三光(株)製「HCA−HQ」、10-(2,5-ジヒドロキシフェニル)-10-ヒドロ-9-オキサ-10-フォスファフェナンスレン-10-オキサイド、平均粒径2μm)5部、アミノシラン系カップリング剤(信越化学工業(株)製「KBM573」)で表面処理された球形シリカ(平均粒径0.5μm、(株)アドマテックス製「SOC2」、単位面積当たりのカーボン量0.39mg/m2)140部、ポリビニルブチラール樹脂(積水化学工業(株)製「KS−1」、固形分15重量%のエタノールとトルエンの1:1溶液)15部を混合し、高速回転ミキサーで均一に分散して、樹脂ワニス1を調製した。
(2)接着フィルム1の作製
支持体として、厚さ38μmのPETフィルムを用意した。該支持体の表面に、上記(1)で得られた樹脂ワニス1を、乾燥後の熱硬化性樹脂組成物層の厚さが40μmとなるようにダイコーターにて均一に塗布し、80〜120℃(平均100℃)で6分間乾燥させることにより、接着フィルム1を作製した。
Preparation Example 1
(1) Preparation of resin varnish 1 10 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, Mitsubishi Chemical Corporation "jER 828EL"), biphenyl type epoxy resin (epoxy equivalent 269, Nippon Kayaku Co., Ltd. "NC 3000 L" 20 parts, 6 parts of tetrafunctional naphthalene type epoxy resin (epoxy equivalent 163, DIC Corporation “HP 4700”), and phenoxy resin (Mitsubishi Chemical Corporation “YL7553BH30”, MEK having a solid content of 30% by mass A 1: 1 solution of cyclohexanone, 10 parts by weight-average molecular weight 35000, was heated and dissolved in a mixed solvent of 5 parts of MEK, 5 parts of cyclohexanone and 15 parts of solvent naphtha while stirring. After cooling to room temperature, 15 parts of a triazine-containing phenol novolac curing agent (hydroxyl group equivalent weight 125, "LA7054" manufactured by DIC Corporation, 60 mass% solid MEK solution), naphtholic curing agent (hydroxyl content equivalent weight 215) Toho Kasei Co., Ltd. product "SN-485", MEK solution of 60% of solid content 15 parts, Amine-based curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution of 5 mass% of solid content) 1 part 0.3 part of imidazole-based curing accelerator (1-benzyl-2-phenylimidazole, “1B2PZ” manufactured by Shikoku Kasei Kogyo Co., Ltd., MEK solution having a solid content of 5% by mass), a flame retardant (manufactured by Sanko Co., Ltd.) HCA-HQ ", 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (average particle size 2 μm) 5 parts, aminosilane based coupler Grayed agent (Shin-Etsu Chemical Co., Ltd., "KBM573") surface-treated with spherical silica (average particle size 0.5 [mu] m, Co. Admatechs Co. "SOC2" carbon amount per unit area 0.39 mg / m 2 ) 140 parts of polyvinyl butyral resin ("KS-1" manufactured by Sekisui Chemical Co., Ltd., 15 parts by weight of ethanol and toluene with a solid content of 15% by weight) are mixed and uniformly dispersed by a high-speed rotary mixer The resin varnish 1 was prepared.
(2) Preparation of Adhesive Film 1 As a support, a PET film having a thickness of 38 μm was prepared. The resin varnish 1 obtained in the above (1) is uniformly coated on the surface of the support by a die coater so that the thickness of the thermosetting resin composition layer after drying is 40 μm, The adhesive film 1 was produced by drying at 120 degreeC (average 100 degreeC) for 6 minutes.
〔作製例2〕
ナフトール系硬化剤(水酸基当量215、東都化成(株)製「SN−485」、固形分60%のMEK溶液)15部に代えて、ジシクロペンタジエン型フェノールノボラック型硬化剤(水酸基当量192、群栄化学工業(株)製「GDP−6140」、固形分50%のMEK溶液)16部を使用した以外は、作製例1と同様にして樹脂ワニス2を調製した。
得られた樹脂ワニス2を使用して、作製例1と同様にして接着フィルム2を作製した。
Preparation Example 2
Dicyclopentadiene type phenol novolac type curing agent (hydroxyl equivalent weight 192, group) instead of 15 parts of naphtholic curing agent (hydroxyl equivalent weight 215, Toho Kasei Co., Ltd. “SN-485”, MEK solution with solid content of 60%) A resin varnish 2 was prepared in the same manner as in Preparation Example 1 except that 16 parts of “GDP-6140” (manufactured by Eisai Chemical Co., Ltd., MEK solution with a solid content of 50%) was used.
An adhesive film 2 was produced in the same manner as in Production Example 1 using the obtained resin varnish 2.
〔作製例3〕
(1)樹脂ワニス3の調製
液状ビスフェノールA型エポキシ樹脂(エポキシ当量180、三菱化学(株)製「jER828EL」)15部、及びビフェニル型エポキシ樹脂(エポキシ当量291、日本化薬(株)製「NC3000H」)15部を、MEK15部とシクロヘキサノン15部の混合溶媒に撹拌しながら加熱溶解させた。室温まで冷却した後、そこへ、活性エステル系硬化剤(活性エステル当量223、DIC(株)製「HPC−8000−65T」、固形分65%のトルエン溶液)20部、トリアジン含有クレゾールノボラック樹脂(フェノール当量151、DIC(株)製「LA3018−50P」、固形分50%の2-メトキシプロパノール溶液)6部、アミン系硬化促進剤(4−ジメチルアミノピリジン(DMAP)、固形分5質量%のMEK溶液)1部、アミノシラン系カップリング剤(信越化学工業(株)製「KBM573」)で表面処理された球形シリカ(平均粒径0.5μm、(株)アドマテックス製「SOC2」、単位面積当たりのカーボン量0.39mg/m2)110部、フェノキシ樹脂(三菱化学(株)製「YL7553BH30」、固形分30質量%のMEKとシクロヘキサノンの1:1溶液、重量平均分子量35000)7部を混合し、高速回転ミキサーで均一に分散して、樹脂ワニス3を調製した。
(2)接着フィルム3の作製
上記(1)で得た樹脂ワニス3を用いて、作製例1と同様にして接着フィルム3を作製した。
[Preparation Example 3]
(1) Preparation of resin varnish 3 15 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, Mitsubishi Chemical Corporation "jER 828EL"), and biphenyl type epoxy resin (epoxy equivalent 291; Nippon Kayaku Co., Ltd. " 15 parts of NC 3000 H ′ ′) was heated and dissolved in a mixed solvent of 15 parts of MEK and 15 parts of cyclohexanone with stirring. After cooling to room temperature, 20 parts of active ester curing agent (active ester equivalent 223, “HPC-8000-65T”, 65% solid solution in toluene, made by DIC Co., Ltd.), triazine-containing cresol novolac resin ( Phenol equivalent weight 151, DIC Corporation “LA3018-50P”, 6 parts of solid content 50% 2-methoxypropanol solution, amine curing accelerator (4-dimethylaminopyridine (DMAP), solid content 5% by mass 1 part MEK solution, spherical silica (average particle diameter 0.5 μm, surface-treated with an aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd. “KBM 573”), average particle diameter 0.5 μm, “SOC 2” manufactured by Admatechs Co., Ltd., unit area carbon amount 0.39 mg / m 2) 110 parts per, phenoxy resin (Mitsubishi Chemical Co., Ltd. "YL7553BH30" Solid content 30% by weight of MEK and cyclohexanone 1: 1 solution, the weight average molecular weight 35000) 7 parts were mixed, and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish 3.
(2) Production of Adhesive Film 3 An adhesive film 3 was produced in the same manner as in Production Example 1 using the resin varnish 3 obtained in (1) above.
〔作製例4〕
アミノシラン系カップリング剤(信越化学工業(株)製「KBM573」)で表面処理された球形シリカ(平均粒径0.5μm、(株)アドマテックス製「SOC2」、単位面積当たりのカーボン量0.39mg/m2)の配合量を、140部から200部へと変更した以外は、作製例1と同様にして樹脂ワニス4を調製した。
得られた樹脂ワニス4を使用して、作製例1と同様にして接着フィルム4を作製した。
[Preparation Example 4]
Spherical silica (average particle diameter 0.5 μm, average particle diameter 0.5 μm, “SOC2” manufactured by Admatechs Co., Ltd.) surface-treated with an aminosilane-based coupling agent (“KBM 573” manufactured by Shin-Etsu Chemical Co., Ltd.) A resin varnish 4 was prepared in the same manner as in Preparation Example 1 except that the compounding amount of 39 mg / m 2 ) was changed from 140 parts to 200 parts.
An adhesive film 4 was produced in the same manner as in Production Example 1 using the obtained resin varnish 4.
〔作製例5〕
アミン系硬化促進剤(4−ジメチルアミノピリジン(DMAP)、固形分5質量%のMEK溶液)1部及びイミダゾール系硬化促進剤(1−ベンジル−2−フェニルイミダゾール、四国化成工業(株)製「1B2PZ」、固形分5質量%のMEK溶液)0.3部に代えて、リン系硬化促進剤(テトラフェニルホスホニウムテトラ−p−トリルボレート、北興産業(株)製「TPP−MK」)2部を使用した以外は、作製例1と同様にして樹脂ワニス5を調製した。
得られた樹脂ワニス5を使用して、作製例1と同様にして接着フィルム5を作製した。
[Preparation Example 5]
1 part of amine-based curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5% by mass) and imidazole-based curing accelerator (1-benzyl-2-phenylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.) 1B2PZ, 2 parts of phosphorus-based curing accelerator (tetraphenylphosphonium tetra-p-tolylborate, manufactured by Hokuko Sangyo Co., Ltd. "TPP-MK") in place of 0.3 part of MEK solution having a solid content of 5% by mass A resin varnish 5 was prepared in the same manner as in Preparation Example 1 except that the above was used.
An adhesive film 5 was produced in the same manner as in Production Example 1 using the obtained resin varnish 5.
〔作製例6〕
フェノキシ樹脂(三菱化学(株)製「YL7553BH30」、固形分30質量%のMEKとシクロヘキサノンの1:1溶液、重量平均分子量35000)10部を使用しなかった以外は、作製例1と同様にして樹脂ワニス6を調製した。
得られた樹脂ワニス6を使用して、作製例1と同様にして接着フィルム6を作製した。
[Preparation Example 6]
In the same manner as in Preparation Example 1 except that 10 parts of phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corp., a 1: 1 solution of MEK having a solid content of 30% by mass, and a weight average molecular weight of 35000) was not used. Resin varnish 6 was prepared.
An adhesive film 6 was produced in the same manner as in Production Example 1 using the obtained resin varnish 6.
作製した接着フィルム1〜6について、熱硬化性樹脂組成物層の組成を表1にまとめて示す。 The composition of the thermosetting resin composition layer is collectively shown in Table 1 about the produced adhesive films 1 to 6.
<実施例1>
接着フィルム1を用いて、上記〔測定・評価用サンプルの調製〕の手順に従って、プリント配線板を製造した。各評価結果を表2に示す。
Example 1
A printed wiring board was manufactured using the adhesive film 1 in accordance with the procedure of the above-mentioned [Preparation of sample for measurement and evaluation]. Each evaluation result is shown in Table 2.
<実施例2>
接着フィルム2を用いて、上記〔測定・評価用サンプルの調製〕の手順に従って、プリント配線板を製造した。各評価結果を表2に示す。
Example 2
Using the adhesive film 2, a printed wiring board was manufactured according to the procedure of the above-mentioned [Preparation of sample for measurement and evaluation]. Each evaluation result is shown in Table 2.
<実施例3>
接着フィルム3を用いて、上記〔測定・評価用サンプルの調製〕の手順に従って、プリント配線板を製造した。各評価結果を表2に示す。
Example 3
A printed wiring board was manufactured using the adhesive film 3 in accordance with the procedure of the above-mentioned [Preparation of sample for measurement and evaluation]. Each evaluation result is shown in Table 2.
<実施例4>
接着フィルム4を用いて、上記〔測定・評価用サンプルの調製〕の手順に従って、プリント配線板を製造した。各評価結果を表2に示す。
Example 4
A printed wiring board was manufactured using the adhesive film 4 in accordance with the procedure of the above-mentioned [Preparation of sample for measurement and evaluation]. Each evaluation result is shown in Table 2.
<実施例5>
接着フィルム2を用いて、上記〔測定・評価用サンプルの調製〕の手順に従って、プリント配線板を製造した。各評価結果を表2に示す。
Example 5
Using the adhesive film 2, a printed wiring board was manufactured according to the procedure of the above-mentioned [Preparation of sample for measurement and evaluation]. Each evaluation result is shown in Table 2.
<比較例1>
接着フィルム5を用いて、上記〔測定・評価用サンプルの調製〕の手順に従って、プリント配線板を製造した。各評価結果を表2に示す。
Comparative Example 1
A printed wiring board was manufactured using the adhesive film 5 in accordance with the procedure of the above-mentioned [Preparation of samples for measurement and evaluation]. Each evaluation result is shown in Table 2.
<比較例2>
接着フィルム6を用いて、上記〔測定・評価用サンプルの調製〕の手順に従って、プリント配線板を製造した。各評価結果を表2に示す。
Comparative Example 2
A printed wiring board was manufactured using the adhesive film 6 in accordance with the procedure of the above-mentioned [Preparation of samples for measurement and evaluation]. Each evaluation result is shown in Table 2.
表2より、X線光電子分光法により測定した、表面のSi量が25atom%以下であり、かつO量が25atom%以上である実施例1〜5の粗化硬化体は、表面の粗度が低く且つ導体層に対して優れた剥離強度を呈することが確認される。一方、表面のSi原子とO原子の割合が所望の範囲にない比較例1及び2の粗化硬化体は、表面粗度が高いにもかかわらず、導体層に対して十分な剥離強度を呈しないことが確認される。 From Table 2, the roughened cured products of Examples 1 to 5 in which the amount of Si on the surface is 25 atom% or less and the amount of O is 25 atom% or more measured by X-ray photoelectron spectroscopy have a surface roughness of It is confirmed to exhibit low and excellent peel strength to the conductor layer. On the other hand, the roughened cured products of Comparative Examples 1 and 2 in which the ratio of Si atoms to O atoms in the surface is not within the desired range exhibit sufficient peel strength to the conductor layer despite the high surface roughness. Not be confirmed.
Claims (9)
前記無機充填材がシリカであり、
X線光電子分光法により測定した、表面のSi量が25atom%以下であり、かつ表面のO量が25atom%以上であり、
前記熱硬化性樹脂組成物がフェノキシ樹脂を含む、
粗化硬化体(ただし、前記熱硬化性樹脂組成物が活性エステル系硬化剤を含む場合を除く)。 A roughened cured body obtained by roughening a thermosetting body of a thermosetting resin composition having an inorganic filler content of 50% by mass or more,
The inorganic filler is silica,
The amount of Si on the surface measured by X-ray photoelectron spectroscopy is 25 atom% or less, and the amount of O on the surface is 25 atom% or more,
The thermosetting resin composition including a phenoxy resin,
Roughened cured product (except in the case where the thermosetting resin composition contains an active ester curing agent).
前記無機充填材がシリカであり、
X線光電子分光法により測定した、表面のSi量が25atom%以下であり、かつ表面のO量が25atom%以上であり、
前記熱硬化性樹脂組成物が、熱硬化性樹脂組成物中の不揮発成分の合計を100質量%としたときに熱可塑性樹脂を0.1質量%〜20質量%含む、
粗化硬化体(ただし、前記熱硬化性樹脂組成物が活性エステル系硬化剤を含む場合を除く)。 A roughened cured body obtained by roughening a thermosetting body of a thermosetting resin composition having an inorganic filler content of 50% by mass or more,
The inorganic filler is silica,
The amount of Si on the surface measured by X-ray photoelectron spectroscopy is 25 atom% or less, and the amount of O on the surface is 25 atom% or more,
The thermosetting resin composition, 0.1 weight thermoplastic resin% to 20 wt% including when the total of the nonvolatile components of the thermosetting resin composition is 100 mass%,
Roughened cured product (except in the case where the thermosetting resin composition contains an active ester curing agent).
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