JP2017132904A - Addition reaction curable resin composition and optical semiconductor device - Google Patents
Addition reaction curable resin composition and optical semiconductor device Download PDFInfo
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- 238000007259 addition reaction Methods 0.000 title claims abstract description 40
- 239000011342 resin composition Substances 0.000 title claims abstract description 33
- 239000004065 semiconductor Substances 0.000 title claims abstract description 16
- 230000003287 optical effect Effects 0.000 title claims abstract description 15
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 40
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims abstract description 38
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- 150000007973 cyanuric acids Chemical class 0.000 claims abstract description 20
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 14
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 11
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 3
- 239000004954 Polyphthalamide Substances 0.000 abstract description 9
- 229920006375 polyphtalamide Polymers 0.000 abstract description 9
- 229920000647 polyepoxide Polymers 0.000 abstract description 8
- 239000003822 epoxy resin Substances 0.000 abstract description 7
- 239000005062 Polybutadiene Substances 0.000 abstract description 5
- 229920002857 polybutadiene Polymers 0.000 abstract description 5
- -1 polysiloxane Polymers 0.000 description 16
- 125000000962 organic group Chemical group 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000003961 organosilicon compounds Chemical class 0.000 description 5
- 230000035939 shock Effects 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 239000002683 reaction inhibitor Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XAJOPMVSQIBJCW-SNAWJCMRSA-N (E)-3-penten-1-yne Chemical compound C\C=C\C#C XAJOPMVSQIBJCW-SNAWJCMRSA-N 0.000 description 1
- HMVBQEAJQVQOTI-SOFGYWHQSA-N (e)-3,5-dimethylhex-3-en-1-yne Chemical compound CC(C)\C=C(/C)C#C HMVBQEAJQVQOTI-SOFGYWHQSA-N 0.000 description 1
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Abstract
Description
本発明は、ＬＥＤ（発光ダイオード）のパッケージ（基板）に使用されることが多いポリフタルアミド等の熱可塑性樹脂及びエポキシ等の熱硬化性樹脂の双方に良好な接着性を有する付加反応硬化型樹脂組成物及び光半導体装置に関する。 The present invention is an addition reaction curable type having good adhesion to both thermoplastic resins such as polyphthalamide and thermosetting resins such as epoxy, which are often used in LED (light emitting diode) packages (substrates). The present invention relates to a resin composition and an optical semiconductor device.
従来、本出願人は、ポリフタルアミド樹脂などの難接着性基材に対して優れた密着性を有するＬＥＤなどの光半導体封止用の組成物として、ＳｉＨ基と反応性を有する炭素−炭素二重結合を１分子中に少なくとも２個含有し且つ一の珪素原子に一のフェニル基が結合したオルガノポリシロキサン（ａ）、１分子中に少なくとも２個のＳｉＨ基を含有し且つ一の珪素原子に一のフェニル基が結合したオルガノ水素ポリシロキサン（ｂ）、付加反応触媒（ｃ）と、（メタ）アクリロイル基含有シランカップリング剤（ｄ１）および脂環式エポキシ基含有シランカップリング剤（ｄ２）の反応物（ｄ）を含有することを特徴とする付加型シリコーン樹脂組成物を提案している（特許文献１）。 Conventionally, as a composition for sealing an optical semiconductor such as an LED having excellent adhesion to a hardly-adhesive substrate such as a polyphthalamide resin, the present applicant has used carbon-carbon having reactivity with SiH groups. Organopolysiloxane having at least two double bonds in one molecule and one phenyl group bonded to one silicon atom (a), containing at least two SiH groups in one molecule and one silicon Organohydrogenpolysiloxane (b) having one phenyl group bonded to an atom, an addition reaction catalyst (c), a (meth) acryloyl group-containing silane coupling agent (d1), and an alicyclic epoxy group-containing silane coupling agent ( The addition type silicone resin composition characterized by containing the reaction product (d) of d2) is proposed (Patent Document 1).
また、同様に、ＳｉＨ基と反応性を有する炭素−炭素二重結合を１分子中に少なくとも２個含有するオルガノポリシロキサン（ａ）、１分子中に少なくとも２個のＳｉＨ基を含有するオルガノ水素ポリシロキサン（ｂ）、付加反応触媒（ｃ）と、（メタ）アクリロイル基含有シランカップリング剤（ｄ１）およびエポキシ基含有シランカップリング剤（ｄ２）の反応物（ｄ）と、トリス（トリアルコキシシリルプロピル）イソシアヌレート（ｅ）とを含有することを特徴とする付加型シリコーン樹脂組成物を提案している（特許文献２）。 Similarly, organopolysiloxane (a) containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and organohydrogen containing at least two SiH groups in one molecule. Reaction product (d) of polysiloxane (b), addition reaction catalyst (c), (meth) acryloyl group-containing silane coupling agent (d1) and epoxy group-containing silane coupling agent (d2), and tris (trialkoxy) An addition-type silicone resin composition characterized by containing (silylpropyl) isocyanurate (e) has been proposed (Patent Document 2).
しかしながら、これらの付加反応硬化型シリコーン樹脂組成物は、ポリフタルアミド樹脂に対する密着性は良好であっても、エポキシ樹脂に対する密着性が不十分な場合があり、特には実際の使用条件である点灯に伴う熱冷繰り返しに係る熱衝撃を与えるとこれらのパッケージから剥離や脱落を生じる場合があり、結果として光半導体素子の輝度低下や不灯が生じるという課題がある。 However, even though these addition reaction curable silicone resin compositions have good adhesion to the polyphthalamide resin, they may have insufficient adhesion to the epoxy resin. When a thermal shock associated with repeated heat-cooling is caused, peeling or dropping may occur from these packages, and as a result, there is a problem in that the brightness of the optical semiconductor element is reduced or unlit.
本発明が解決しようとする課題は、ＬＥＤのパッケージに使用されるポリフタルアミド樹脂やエポキシ樹脂の双方に対する密着性が良好であり、硬化物が無色透明である付加反応硬化型樹脂組成物及び光半導体装置を提供することにある。 The problem to be solved by the present invention is an addition reaction curable resin composition and light that have good adhesion to both polyphthalamide resin and epoxy resin used in LED packages, and the cured product is colorless and transparent. It is to provide a semiconductor device.
上記課題を解決するため、請求項１記載の発明は、
ヒドロシリル化反応によりＳｉＨ基と反応するアルケニル基を１分子中に２個以上有するオルガノポリシロキサン（Ａ）と、
１分子中に少なくとも２個のＳｉＨ基を有するオルガノ水素ポリシロキサン（Ｂ）と、
ヒドロシリル化反応によりＳｉＨ基と反応する官能基を1分子中に少なくとも１個以上とエポキシ基を１分子中に少なくとも１個以上有するイソシアヌル酸誘導体（Ｃ）と、
エポキシ基を１分子中に少なくとも１個以上有するポリブタジエン変性樹脂（Ｄ）と、
付加反応に必要な硬化触媒（Ｅ）と、から成る付加反応硬化型樹脂組成物であり、
オルガノポリシロキサン（Ａ）とオルガノ水素ポリシロキサン（Ｂ）は、
１分子中に少なくとも１個の（Ｃ６Ｈ５）ＳｉＯ３／２ 単位を有するオルガノポリシロキサン（Ａ１）から成るオルガノポリシロキサン（Ａ）と、下記組成式（I）で表される直鎖状のオルガノ水素ポリシロキサン（Ｂ１）から成るオルガノ水素ポリシロキサン（Ｂ）であるか、
（ＨＲ２ＳｉＯ１／２）ｍ（Ｒ２ＳｉＯ２／２）ｎ[Ｒのうち少なくとも１個はフェニル基であり、ｍは２、ｎは１以上の整数］ （Ｉ）
直鎖状のオルガノポリシロキサン（Ａ２）から成るオルガノポリシロキサン（Ａ）と、１分子中に少なくとも１個の（Ｃ６Ｈ５）ＳｉＯ３／２単位を有するオルガノ水素ポリシロキサン（Ｂ２）から成るオルガノ水素ポリシロキサン（Ｂ）である、
ことを特徴とする付加反応硬化型樹脂組成物を提供する。
In order to solve the above problem, the invention according to claim 1
Organopolysiloxane (A) having two or more alkenyl groups in one molecule that react with SiH groups by hydrosilylation reaction;
An organohydrogenpolysiloxane (B) having at least two SiH groups in one molecule;
An isocyanuric acid derivative (C) having at least one functional group that reacts with SiH groups by hydrosilylation reaction in one molecule and at least one epoxy group in one molecule;
A polybutadiene-modified resin (D) having at least one epoxy group in one molecule;
An addition reaction curable resin composition comprising a curing catalyst (E) necessary for the addition reaction,
Organopolysiloxane (A) and organohydrogenpolysiloxane (B) are:
Organopolysiloxane (A) composed of organopolysiloxane (A1) having at least one (C 6 H 5 ) SiO 3/2 unit in one molecule, and a straight chain represented by the following composition formula (I) Or an organohydrogenpolysiloxane (B) comprising the organohydrogenpolysiloxane (B1) of
(HR 2 SiO 1/2 ) m (R 2 SiO 2/2 ) n [At least one of R is a phenyl group, m is 2, and n is an integer of 1 or more] (I)
Organopolysiloxane (A) composed of linear organopolysiloxane (A2) and organohydrogenpolysiloxane (B2) having at least one (C 6 H 5 ) SiO 3/2 unit in one molecule An organohydrogenpolysiloxane (B),
An addition reaction curable resin composition is provided.
また、請求項２記載の発明は、オルガノポリシロキサン（Ａ）とイソシアヌル酸誘導体（Ｃ）とポリブタジエン変性樹脂（Ｄ）の全アルケニル基に対するオルガノ水素ポリシロキサン（Ｂ）の珪素原子結合水素基のモル比が０．１〜４．０であり、オルガノポリシロキサン（Ａ）とオルガノ水素ポリシロキサン（Ｂ）とイソシアヌル酸誘導体（Ｃ）の合計１００重量部に対してイソシアヌル酸誘導体（Ｃ）は０．１〜５０重量部であることを特徴とする請求項１記載の付加反応硬化型樹脂組成物を提供する。 Further, the invention according to claim 2 is directed to the moles of silicon-bonded hydrogen groups of organohydrogenpolysiloxane (B) with respect to all alkenyl groups of organopolysiloxane (A), isocyanuric acid derivative (C) and polybutadiene-modified resin (D). The isocyanuric acid derivative (C) has a ratio of 0.1 to 4.0, and the isocyanuric acid derivative (C) has a value of 0.1 with respect to a total of 100 parts by weight of the organopolysiloxane (A), the organohydrogenpolysiloxane (B), and the isocyanuric acid derivative (C). The addition reaction curable resin composition according to claim 1, which is 1 to 50 parts by weight.
また、請求項３記載の発明は、オルガノポリシロキサン（Ａ）とオルガノ水素ポリシロキサン（Ｂ）とイソシアヌル酸誘導体（Ｃ）の合計１００重量部に対してポリブタジエン変性樹脂（Ｄ）は０．１〜５０重量部であることを特徴とする請求項１又は請求項２に記載の付加反応硬化型樹脂組成物を提供する。 The invention according to claim 3 is characterized in that the polybutadiene-modified resin (D) is 0.1 to 0.1 parts by weight with respect to a total of 100 parts by weight of the organopolysiloxane (A), the organohydrogenpolysiloxane (B), and the isocyanuric acid derivative (C). The addition reaction curable resin composition according to claim 1 or 2, which is 50 parts by weight.
また、請求項４記載の発明は、オルガノ水素ポリシロキサン（Ｂ）は珪素原子に結合している水素原子の含有量が１．０ｍｍｏｌ／ｇ〜２０．０ｍｍｏｌ／ｇであることを特徴とする請求項１乃至請求項３記載の付加反応硬化型樹脂組成物を提供する。 The invention according to claim 4 is characterized in that the content of hydrogen atoms bonded to silicon atoms in the organohydrogenpolysiloxane (B) is 1.0 mmol / g to 20.0 mmol / g. An addition reaction curable resin composition according to any one of claims 1 to 3 is provided.
また、請求項５記載の発明は、さらに接着性付与剤（Ｆ）を含むことを特徴とする請求項１乃至請求項４のいずれかに記載の付加反応硬化型樹脂組成物を提供する。 The invention according to claim 5 provides the addition reaction curable resin composition according to any one of claims 1 to 4, further comprising an adhesion-imparting agent (F).
また、請求項６記載の発明は、請求項１乃至請求項５のいずれかに記載の付加反応硬化型樹脂組成物の硬化物で光半導体素子が封止されていることを特徴とする光半導体装置を提供する。 According to a sixth aspect of the present invention, there is provided an optical semiconductor wherein the optical semiconductor element is sealed with a cured product of the addition reaction curable resin composition according to any one of the first to fifth aspects. Providing equipment.
本発明の付加反応硬化型樹脂組成物は、ＬＥＤのパッケージに使用されるポリフタルアミド樹脂及びエポキシ樹脂の双方に対する密着性が良好であり、特に実際の使用条件を模した、熱冷繰り返しに係る熱衝撃を与えてもこれらのパッケージから剥離や脱落を生じることがなく、結果として本発明の付加反応硬化型樹脂組成物で封止された光半導体素子の輝度低下や不灯が生じることがないという効果がある。また本発明の付加反応硬化型樹脂組成物の硬化物は無色透明であるという効果がある。 The addition reaction curable resin composition of the present invention has good adhesion to both a polyphthalamide resin and an epoxy resin used in LED packages, and is particularly related to repeated heat cooling, which simulates actual use conditions. Even if a thermal shock is given, these packages do not peel off or fall off, and as a result, the brightness of the optical semiconductor element encapsulated with the addition reaction curable resin composition of the present invention and no unlighting do not occur. There is an effect. Further, the cured product of the addition reaction curable resin composition of the present invention has an effect of being colorless and transparent.
また、請求項６記載の光半導体装置は、そのパッケージがポリフタルアミド樹脂又はエポキシ樹脂であっても、封止に使用されている本発明の付加反応硬化型樹脂組成物の硬化物が剥離や脱落を生じることが無く、輝度低下や不灯が生じることがないという効果がある。また封止に使用されている付加反応硬化型樹脂組成物は無色透明であるため高輝度であるという効果がある。 Moreover, the optical semiconductor device according to claim 6, even if the package is a polyphthalamide resin or an epoxy resin, the cured product of the addition reaction curable resin composition of the present invention used for sealing is peeled off or peeled off. There is an effect that no dropout occurs and no reduction in brightness or unlighting occurs. Moreover, since the addition reaction curable resin composition used for sealing is colorless and transparent, it has an effect of high brightness.
以下、本発明に係る付加反応硬化型樹脂組成物について具体的に説明する。 Hereinafter, the addition reaction curable resin composition according to the present invention will be described in detail.
＜オルガノポリシロキサン（Ａ）及びオルガノ水素ポリシロキサン（Ｂ）＞
本発明に使用するオルガノポリシロキサン（Ａ）はヒドロシリル化反応によりＳｉＨ基と反応するビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、イソブテニル基、ヘキセニル基などの炭素−炭素二重結合であるアルケニル基を１分子中に２個以上有すると共に、１分子中に少なくとも１個の（Ｃ６Ｈ５）ＳｉＯ３／２単位（Ｔ単位）を有するオルガノポリシロキサン（Ａ１）であるか、又は同様にヒドロシリル化反応によりＳｉＨ基と反応するビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、イソブテニル基、ヘキセニル基などの炭素−炭素二重結合であるアルケニル基を１分子中に２個以上有すると共に、中間単位がＤ単位から成る直鎖状のオルガノポリシロキサン（Ａ２）である。末端や繰り返し単位中の珪素に結合したオルガノ基としては、メチル基、エチル基、フェニル基などが例示される。オルガノポリシロキサン（Ａ１）の具体例としては、分岐鎖状のメチルフェニルビニルポリシロキサンが挙げられ、オルガノポリシロキサン（Ａ２）の具体例としては直鎖状のメチルフェニルビニルポリシロキサンが挙げられる。
<Organopolysiloxane (A) and organohydrogenpolysiloxane (B)>
The organopolysiloxane (A) used in the present invention is a carbon-carbon double bond such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, and hexenyl group that reacts with SiH group by hydrosilylation reaction. Or an organopolysiloxane (A1) having two or more alkenyl groups in one molecule and at least one (C 6 H 5 ) SiO 3/2 unit (T unit) in one molecule, Alternatively, an alkenyl group that is a carbon-carbon double bond such as a vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, or hexenyl group that reacts with the SiH group by hydrosilylation reaction in one molecule. It is a linear organopolysiloxane (A2) having two or more and having an intermediate unit composed of D units. Examples of the organo group bonded to silicon in the terminal or repeating unit include a methyl group, an ethyl group, and a phenyl group. Specific examples of the organopolysiloxane (A1) include branched methylphenylvinylpolysiloxane, and specific examples of the organopolysiloxane (A2) include linear methylphenylvinylpolysiloxane.
一方、オルガノ水素ポリシロキサン（Ｂ）は、１分子中に少なくとも２個のＳｉＨ基を有し、少なくと末端又は繰返し構造中において、２個以上のＳｉＨ基を含有する。珪素原子に結合している水素原子の含有量は１．０ｍｍｏｌ／ｇ〜２０．０ｍｍｏｌ／ｇであることが好ましく、１．０ｍｍｏｌ／ｇ以上であると硬化性がよくなり、硬さも得やすくなる。水素原子の含有量が２０．０ｍｍｏｌ／ｇ超であると、硬化物表面にタックが生じやすくなる。良好な硬さを得るためには水素原子含有比率を１.５ｍｍｏｌ／ｇ以上であることがより好ましい。タックを生じ難くするためには水素原子含有量は１０．０ｍｍｏｌ／ｇ未満であることがより好ましい。珪素原子に結合するオルガノ基としては、メチル基、エチル基、フェニル基などが例示される。 On the other hand, the organohydrogenpolysiloxane (B) has at least two SiH groups in one molecule and at least two or more SiH groups in the terminal or repeating structure. The content of hydrogen atoms bonded to silicon atoms is preferably 1.0 mmol / g to 20.0 mmol / g, and if it is 1.0 mmol / g or more, curability is improved and hardness is easily obtained. . When the content of hydrogen atoms exceeds 20.0 mmol / g, tackiness is likely to occur on the surface of the cured product. In order to obtain good hardness, the hydrogen atom content ratio is more preferably 1.5 mmol / g or more. In order to make it difficult for tackiness to occur, the hydrogen atom content is more preferably less than 10.0 mmol / g. Examples of the organo group bonded to the silicon atom include a methyl group, an ethyl group, and a phenyl group.
このようなオルガノ水素ポリシロキサン（Ｂ）のうち、上記オルガノポリシロキサン（Ａ）と組み合わされるオルガノ水素ポリシロキサン（Ｂ）は、オルガノポリシロキサン（Ａ１）から成るオルガノポリシロキサン（Ａ）に対しては、下記組成式（I）で表される直鎖状のオルガノ水素ポリシロキサン（Ｂ１）から成るオルガノ水素ポリシロキサン（Ｂ）であり、
（ＨＲ２ＳｉＯ１／２）ｍ（Ｒ２ＳｉＯ２／２）ｎ[Ｒのうち少なくとも１個はフェニル基であり、ｍは２、ｎは１以上の整数］ （I）
上記オルガノポリシロキサン（Ａ２）から成るオルガノポリシロキサン（Ａ）に組み合わされるオルガノ水素ポリシロキサン（Ｂ）は、１分子中に少なくとも１個の（Ｃ６Ｈ５）ＳｉＯ３／２単位（Ｔ単位）を有するオルガノ水素ポリシロキサン（Ｂ２）から成るオルガノ水素ポリシロキサン（Ｂ）である。オルガノ水素ポリシロキサン（Ｂ１）の具体例としては、直鎖状のメチルフェニル水素ポリシロキサンが挙げられ、オルガノ水素ポリシロキサン（Ｂ２）の具体例としては、分岐鎖状のメチルフェニル水素ポリシロキサンが挙げられる。
Among such organohydrogenpolysiloxanes (B), the organohydrogenpolysiloxane (B) combined with the organopolysiloxane (A) is an organopolysiloxane (A) composed of the organopolysiloxane (A1). , An organohydrogen polysiloxane (B) composed of a linear organohydrogen polysiloxane (B1) represented by the following composition formula (I):
(HR 2 SiO 1/2 ) m (R 2 SiO 2/2 ) n [At least one of R is a phenyl group, m is 2, and n is an integer of 1 or more] (I)
The organohydrogenpolysiloxane (B) combined with the organopolysiloxane (A) comprising the organopolysiloxane (A2) is at least one (C 6 H 5 ) SiO 3/2 unit (T unit) in one molecule. An organohydrogen polysiloxane (B) comprising an organohydrogen polysiloxane (B2) having Specific examples of the organohydrogenpolysiloxane (B1) include linear methylphenylhydrogenpolysiloxane, and specific examples of the organohydrogenpolysiloxane (B2) include branched methylphenylhydrogenpolysiloxane. It is done.
＜イソシアヌル酸誘導体（Ｃ）＞
本発明に使用するイソシアヌル酸誘導体（Ｃ）は、ヒドロシリル化反応によりＳｉＨ基と反応する官能基を1分子中に少なくとも１個以上とエポキシ基を１分子中に少なくとも１個以上有し、例えば下記一般式（ＩＩ）で示される化合物である。
<Isocyanuric acid derivative (C)>
The isocyanuric acid derivative (C) used in the present invention has at least one functional group that reacts with the SiH group by hydrosilylation reaction in one molecule and at least one epoxy group in one molecule. It is a compound shown by general formula (II).
上記式（ＩＩ）中、Ｒ１は炭素数１〜５０の一価の有機基であって、３個のＲ１のうち少なくとも１個はＳｉＨ基と反応する炭素−炭素二重結合を含む基であり、３個のＲ１のうち少なくとも１個はエポキシ基である。これらに該当するイソシアヌル酸誘導体（Ｃ）としては、ジアリルモノグリシジルイソシアヌレート、モノアリルジグリシジルイソシアヌレートがある。 In the above formula (II), R 1 is a monovalent organic group having 1 to 50 carbon atoms, and at least one of the three R 1 groups contains a carbon-carbon double bond that reacts with a SiH group. And at least one of the three R 1 is an epoxy group. Examples of the isocyanuric acid derivative (C) corresponding to these include diallyl monoglycidyl isocyanurate and monoallyl diglycidyl isocyanurate.
イソシアヌル酸誘導体（Ｃ）の配合量は、該イソシアヌル酸誘導体（Ｃ）と上記オルガノポリシロキサン（Ａ）とオルガノ水素ポリシロキサン（Ｃ）の合計１００重量部に対して０．１〜５０重量部であることが好ましく、より好ましくは０．２〜２５重量部であり、さらに好ましくは０．５〜１０重量部である。０．１重量部未満では良好な密着を得にくい。５０重量部超では白濁を生じやすく、強度が低下しやすい。０．２重量部未満では密着を得にくい傾向にあり、２５重量部超では白濁を生じやすく、強度が低下しやすい傾向がある。また０．５重量部未満では密着がまだ不十分である。１０重量部超では白濁を生じやすく、強度がまだ不十分になりやすい。 The compounding amount of the isocyanuric acid derivative (C) is 0.1 to 50 parts by weight with respect to a total of 100 parts by weight of the isocyanuric acid derivative (C), the organopolysiloxane (A) and the organohydrogenpolysiloxane (C). It is preferable that it is preferably 0.2 to 25 parts by weight, and more preferably 0.5 to 10 parts by weight. If it is less than 0.1 part by weight, it is difficult to obtain good adhesion. If it exceeds 50 parts by weight, white turbidity tends to occur and the strength tends to decrease. If it is less than 0.2 parts by weight, it tends to be difficult to obtain adhesion, and if it exceeds 25 parts by weight, it tends to cause white turbidity and the strength tends to decrease. If the amount is less than 0.5 parts by weight, the adhesion is still insufficient. If it exceeds 10 parts by weight, white turbidity tends to occur, and the strength tends to be insufficient.
＜ポリブタジエン変性樹脂（Ｄ）＞
本発明に使用するポリブタジエン変性樹脂（Ｄ）は、エポキシ基を１分子中に少なくとも１個以上有し、以下の一般式（ＩＩＩ）で示される、少なくとも１，２−ポリブタジエン構造又は１，４−ポリブタジエン構造のいずれかである化合物のエチレン性不飽和基の一部をエポキシ化して得られるポリブタジエン変性エポキシ化合物である。
<Polybutadiene modified resin (D)>
The polybutadiene-modified resin (D) used in the present invention has at least one epoxy group in one molecule and has at least a 1,2-polybutadiene structure or 1,4-polybutadiene represented by the following general formula (III). It is a polybutadiene-modified epoxy compound obtained by epoxidizing a part of an ethylenically unsaturated group of a compound having any one of polybutadiene structures.
上記式（ＩＩＩ）中、ｎ＝２〜２０、ｎ＋ｍ＝１０〜１０００の整数である。ｎ＜２では、ポリフタルアミド樹脂又はエポキシ樹脂に対する密着性が低下し、ｎ＞２０では、密着力が低下する。 In said formula (III), it is an integer of n = 2-20 and n + m = 10-1000. When n <2, the adhesion to the polyphthalamide resin or the epoxy resin is lowered, and when n> 20, the adhesion is reduced.
ポリブタジエン変性樹脂（Ｄ）の配合量は、オルガノポリシロキサン（Ａ）とオルガノ水素ポリシロキサン（Ｂ）とイソシアヌル酸誘導体（Ｃ）の合計１００重量部に対して０．１〜５０重量部であることが好ましく、より好ましくは０．２〜２５重量部である。さらに好ましくは０．５〜１０重量部である。０．１重量部未満では良好な密着を得にくい。５０重量部超では白濁を生じやすく、強度が低下しやすい。０．２重量部未満では密着を得にくい傾向にあり、２５重量部超では白濁を生じやすく、強度が低下しやすい傾向がある。また０．５重量部未満では密着がまだ不十分である。１０重量部超では白濁を生じやすく、強度が不十分になりやすい。 The compounding quantity of polybutadiene modified resin (D) is 0.1-50 weight part with respect to a total of 100 weight part of organopolysiloxane (A), organohydrogenpolysiloxane (B), and isocyanuric acid derivative (C). Is more preferable, and 0.2 to 25 parts by weight is more preferable. More preferably, it is 0.5 to 10 parts by weight. If it is less than 0.1 part by weight, it is difficult to obtain good adhesion. If it exceeds 50 parts by weight, white turbidity tends to occur and the strength tends to decrease. If it is less than 0.2 parts by weight, it tends to be difficult to obtain adhesion, and if it exceeds 25 parts by weight, it tends to cause white turbidity and the strength tends to decrease. If the amount is less than 0.5 parts by weight, the adhesion is still insufficient. If it exceeds 10 parts by weight, white turbidity tends to occur and the strength tends to be insufficient.
＜付加反応に必要な硬化触媒（Ｅ）＞
付加反応に必要な硬化触媒（Ｅ）は、オルガノポリシロキサン（Ａ）とオルガノ水素ポリシロキサン（Ｂ）とイソシアヌル酸誘導体（Ｃ）及びポリブタジエン変性樹脂（Ｄ）とのヒドロシリル化反応を促進させるために添加され、ヒドロシリル化反応の触媒活性を有する公知の金属、金属化合物、金属錯体などを用いることができる。特に白金、白金化合物、それらの錯体を用いることが好ましい。これらの触媒は単独で使用してもよく、２種以上を併用してもよい。また、助触媒を併用してもよい。付加反応触媒（Ｅ）の配合量は組成物全体に対して１ｐｐｍ〜５０ｐｐｍとすることが好ましく、より好ましくは５〜２０ｐｐｍである。１ｐｐｍ未満では硬化性が低下し十分な硬さが得にくくなり、５０ｐｐｍ超では硬化後の透明性が低下する要因となる。
<Curing catalyst (E) required for addition reaction>
The curing catalyst (E) required for the addition reaction is to promote the hydrosilylation reaction of the organopolysiloxane (A), the organohydrogenpolysiloxane (B), the isocyanuric acid derivative (C) and the polybutadiene-modified resin (D). Known metals, metal compounds, metal complexes and the like which are added and have a catalytic activity for hydrosilylation reaction can be used. In particular, it is preferable to use platinum, a platinum compound, or a complex thereof. These catalysts may be used alone or in combination of two or more. A cocatalyst may be used in combination. The addition amount of the addition reaction catalyst (E) is preferably 1 to 50 ppm, more preferably 5 to 20 ppm with respect to the entire composition. If it is less than 1 ppm, the curability is lowered and it is difficult to obtain sufficient hardness, and if it exceeds 50 ppm, the transparency after curing becomes a factor.
＜接着性付与剤（Ｆ）＞
本組成物には、その接着性を向上させるために接着性付与剤（Ｆ）を含有してもよい。この接着性付与剤としては、エポキシ基またはアルコキシ基含有有機珪素化合物、またはそれらの縮合物を用いても良い。このアルコキシ基としてはメトキシ基、エトキシ基、プロポキシ基、ブトキシ基、メトキシエトキシ基が例示され、特に、メトキシ基であることが好ましい。また、この有機珪素化合物の珪素原子に結合するアルコキシ基以外の基としては、アルキル基、アルケニル基、アリール基、アラルキル基、ハロゲン置換アルキル基等の置換もしくは非置換の一価炭化水素基；３−グリシドキシプロピル基、４−グリシドキシブチル基等のグリシドキシアルキル基；２−(３,４−エポキシシクロヘキシル)エチル基、３−(３,４−エポキシシクロヘキシル)プロピル基等のエポキシシクロヘキシルアルキル基；４−オキシラニルブチル基、８−オキシラニルオクチル基等のオキシラニルアルキル基等のエポキシ基含有一価有機基；３−メタクリロキシプロピル基等のアクリル基含有一価有機基；水素原子が例示される。またこの有機珪素化合物は前記（Ａ）成分又は（Ｂ）成分と反応し得る基を有することが好ましく、具体的には、珪素原子結合アルケニル基または珪素原子結合水素原子を有することが好ましい。また、各種の基材に対して良好な接着性を付与できることから、この有機珪素化合物は一分子中に少なくとも１個のエポキシ基含有一価有機基を有するものであることが好ましい。
<Adhesiveness imparting agent (F)>
The composition may contain an adhesion-imparting agent (F) in order to improve the adhesion. As this adhesion-imparting agent, an epoxy group- or alkoxy group-containing organosilicon compound, or a condensate thereof may be used. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group, and a methoxy group is particularly preferable. The group other than the alkoxy group bonded to the silicon atom of the organosilicon compound includes a substituted or unsubstituted monovalent hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and a halogen-substituted alkyl group; 3 -Glycidoxyalkyl groups such as glycidoxypropyl group and 4-glycidoxybutyl group; epoxies such as 2- (3,4-epoxycyclohexyl) ethyl group and 3- (3,4-epoxycyclohexyl) propyl group Cyclohexylalkyl group; epoxy group-containing monovalent organic group such as oxiranylalkyl group such as 4-oxiranylbutyl group and 8-oxiranyloctyl group; acrylic group-containing monovalent organic group such as 3-methacryloxypropyl group Group; a hydrogen atom is exemplified. The organosilicon compound preferably has a group capable of reacting with the component (A) or the component (B). Specifically, the organosilicon compound preferably has a silicon atom-bonded alkenyl group or a silicon atom-bonded hydrogen atom. Moreover, it is preferable that this organosilicon compound has at least one epoxy group-containing monovalent organic group in one molecule because it can provide good adhesion to various substrates.
本組成物には、その他任意の成分として、３−メチル−１−ブチン−３−オール、３,５−ジメチル−１−ヘキシン−３−オール、エチニルシクロヘキサノール等のアルキンアルコール；３−メチル−３−ペンテン−１−イン、３,５−ジメチル−３−ヘキセン−１−イン等のエンイン化合物；１,３,５,７−テトラメチル−１,３,５,７−テトラビニルシクロテトラシロキサン、１,３,５,７−テトラメチル−１,３,５,７−テトラヘキセニルシクロテトラシロキサン、１，３ジビニルテトラメチルジシロキサン等の脂肪族不飽和結合を有する化合物、ベンゾトリアゾール等の反応抑制剤を含有してもよい。この反応抑制剤は硬化性を抑制しない程度の含有量として（Ａ）成分と（Ｂ）成分と（Ｃ）成分の合計１００重量部に対して０.０００１〜１重量部の範囲内であることが好ましい。 In the present composition, as other optional components, alkyne alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, ethynylcyclohexanol; Enyne compounds such as 3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, compounds having an aliphatic unsaturated bond such as 1,3 divinyltetramethyldisiloxane, reactions of benzotriazole, etc. An inhibitor may be contained. This reaction inhibitor is within a range of 0.0001 to 1 part by weight with respect to a total of 100 parts by weight of the component (A), the component (B), and the component (C) as a content that does not suppress curability. Is preferred.
また、本組成物には、さらに耐熱性を向上させるために酸化防止剤を含有してもよい。この酸化防止剤としては一般的に使用されているものを用いる事ができる。例えばヒンダートフェノール系の他、リン系、ヒンダートアミン系、チオエーテル系酸化防止剤が挙げられる。この酸化防止剤の含有量として（Ａ）成分と（Ｂ）成分と（Ｃ）成分の合計１００重量部に対して０.０００１〜１重量部の範囲内であることが好ましい。 Moreover, in order to improve heat resistance further in this composition, you may contain antioxidant. As the antioxidant, those generally used can be used. For example, in addition to hindered phenols, phosphorus-based, hindered amine-based, and thioether-based antioxidants may be mentioned. The content of the antioxidant is preferably in the range of 0.0001 to 1 part by weight based on 100 parts by weight of the total of the component (A), the component (B), and the component (C).
本発明の請求項６に記載の光半導体装置は、上記請求項１乃至請求項５のいずれかに記載の付加反応硬化型樹脂組成物の硬化物により発光ダイオード（ＬＥＤ）等の光半導体素子が封止されている光半導体装置である。 An optical semiconductor device according to a sixth aspect of the present invention is an optical semiconductor device such as a light emitting diode (LED) made of a cured product of the addition reaction curable resin composition according to any one of the first to fifth aspects. This is a sealed optical semiconductor device.
次に、本発明である付加反応硬化型樹脂組成物について、実施例及び比較例により詳細に説明する。 Next, the addition reaction curable resin composition of the present invention will be described in detail with reference to Examples and Comparative Examples.
＜実施例及び比較例＞
オルガノポリシロキサン（Ａ１）として、末端ＭＶｉ単位で封止され、Ｔ単位を含有し、粘度１８．０Ｐａ．ｓ／２５℃で質量平均分子量が１，５００である分岐鎖状メチルフェニルビニルポリシロキサンを、オルガノポリシロキサン（Ａ２）として、両末端がＭＶｉ単位で封止され、中間単位がＤ単位、ＤＶｉ単位からなり、粘度１０．５Ｐａ．ｓ／２５℃で質量平均分子量が８，９００である直鎖状メチルフェニルビニルポリシロキサンを、オルガノ水素ポリシロキサン（Ｂ１）として、（ＭＨ）２Ｄ１で表される粘度０．０００４Ｐａ．ｓ／２５℃で質量平均分子量が３３２で、珪素原子に結合した水素原子の含有量が６．０１ｍｍｏｌ／ｇの直鎖状メチルフェニル水素オルガノポリシロキサンを、オルガノ水素ポリシロキサン（Ｂ２）として、末端ＭＨ単位で封止され、中間単位がＤ単位、Ｔ単位からなり、粘度５．０Ｐａ・s/２５℃で質量平均分子量が１,５００で、珪素原子に結合した水素原子の含有量が２．００ｍｍｏｌ／ｇの分岐鎖状メチルフェニル水素オルガノポリシロキサンを、、イソシアヌル酸誘導体（Ｃ）として、ジアリルグリシジルイソシアヌレートを、ポリブタジエン変性樹脂（Ｄ）として、エポキシ化ブタジエンＪＰ−１００（上記化学式（ＩＩＩ）中、ｍ＝４〜７、ｍ＋ｎ＝１６〜２５、ＥＥＷ：１９０〜２１０、２２Ｐａｓ／４５℃、商品名、日本曹達社製）を、付加反応に必要な硬化触媒（Ｄ）として、白金―ビニルダイマー錯体（Ｐｔ：１２％ｗｔ）を、接着付与剤（Ｆ）として、２-(３,４-エポキシシクロヘキシル)エチルトリメトキシシランを、反応抑制剤として、１−エチニルシクロヘキサノールを、それぞれ使用し、表１の配合にて均一に混合し実施例又は比較例の付加反応硬化型樹脂組成物を得た。
<Examples and Comparative Examples>
The organopolysiloxane (A1) is sealed with terminal M Vi units, contains T units, and has a viscosity of 18.0 Pa. A branched methylphenylvinylpolysiloxane having a mass average molecular weight of 1,500 at s / 25 ° C. is used as organopolysiloxane (A2), and both ends are sealed with M Vi units, the intermediate units are D units, D It consists of Vi units and has a viscosity of 10.5 Pa.s. A linear methylphenylvinylpolysiloxane having a mass average molecular weight of 8,900 at s / 25 ° C. was used as organohydrogenpolysiloxane (B1), and the viscosity represented by (M H ) 2 D 1 was 0.0004 Pa.s. A linear methylphenylhydrogen organopolysiloxane having a mass average molecular weight of 332 at s / 25 ° C. and a content of hydrogen atoms bonded to silicon atoms of 6.01 mmol / g is referred to as an organohydrogen polysiloxane (B2). Sealed with MH units, the intermediate unit consists of D units and T units, the viscosity is 5.0 Pa · s / 25 ° C., the mass average molecular weight is 1,500, and the content of hydrogen atoms bonded to silicon atoms is 2 An epoxidized butadiene JP-100 (the above chemical formula (III) was prepared by using 0.000 mmol / g of branched methylphenyl hydrogen organopolysiloxane as an isocyanuric acid derivative (C), diallyl glycidyl isocyanurate as a polybutadiene-modified resin (D). ), M = 4-7, m + n = 16-25, EEW: 190-210, 22 Pas / 45 ° C., trade name, Japan 2- (3,4-epoxycyclohexyl) using platinum-vinyl dimer complex (Pt: 12% wt) as an adhesion-imparting agent (F) as a curing catalyst (D) required for the addition reaction Ethyltrimethoxysilane was used as a reaction inhibitor and 1-ethynylcyclohexanol was used, respectively, and uniformly mixed according to the formulation shown in Table 1 to obtain an addition reaction curable resin composition of Examples or Comparative Examples.
ＭＶｉ単位：（ＣＨ３）２（ＣＨ２＝ＣＨ）ＳｉＯ１／２
ＭＨ単位：（ＣＨ３）２ＨＳｉＯ１／２
Ｄ単位：（ＣＨ３）２ＳｉＯ２／２又は（Ｃ６Ｈ５）２ＳｉＯ２／２又は（ＣＨ３）（Ｃ６Ｈ５）ＳｉＯ２／２
ＤＶｉ単位：（ＣＨ３）（ＣＨ２＝ＣＨ）ＳｉＯ２／２
Ｔ単位：（Ｃ６Ｈ５）ＳｉＯ３／２
M Vi unit: (CH 3 ) 2 (CH 2 = CH) SiO 1/2
MH unit: (CH 3 ) 2 HSiO 1/2
D unit: (CH 3 ) 2 SiO 2/2 or (C 6 H 5 ) 2 SiO 2/2 or (CH 3 ) (C 6 H 5 ) SiO 2/2
D Vi unit: (CH 3 ) (CH 2 ═CH) SiO 2/2
T unit: (C 6 H 5 ) SiO 3/2
＜評価項目及び評価方法＞ <Evaluation items and evaluation methods>
＜外観＞
各付加反応硬化型樹脂組成物を１５０℃４時間で硬化させ、厚み６ｍｍの試験体を作成し、２３℃下にて目視にて外観を評価した。
<Appearance>
Each addition reaction curable resin composition was cured at 150 ° C. for 4 hours to prepare a test specimen having a thickness of 6 mm, and the appearance was evaluated visually at 23 ° C.
＜熱衝撃性＞
底部が銀メッキされているポリフタルアミド樹脂基材のＬＥＤパッケージ（外形寸法５０×５０ｍｍ）又は同様に底部が銀メッキされているエポキシ樹脂基材のＬＥＤパッケージ（外形寸法３０×３０ｍｍ）の各々８個に、実施例又は比較例の付加反応硬化型樹脂組成物を充填し、１５０℃４時間で硬化させ試験体とする。該試験体を液層ヒートショック試験機ＴＳＢ-２１（ｅｓｐｅｃ社製）に投入し、１００℃５分→−４０℃５分を１サイクルとして１００サイクルの冷熱衝撃を加えた。その後２３℃に冷却後に各ＬＥＤパッケージから剥離している数を目視にて確認した。
<Thermal shock resistance>
8 each of a polyphthalamide resin-based LED package (outer dimension 50 × 50 mm) with a silver plated bottom or an epoxy resin-based LED package (outer dimension 30 × 30 mm) with a silver plated bottom Each is filled with the addition reaction curable resin composition of Example or Comparative Example and cured at 150 ° C. for 4 hours to obtain a test specimen. The test specimen was put into a liquid layer heat shock tester TSB-21 (manufactured by espec), and 100 cycles of thermal shock were applied, with 100 ° C. 5 minutes → −40 ° C. 5 minutes as one cycle. Thereafter, the number of peeling from each LED package after cooling to 23 ° C. was visually confirmed.
＜評価結果＞
評価結果を表２に示す。
<Evaluation results>
The evaluation results are shown in Table 2.
Claims (6)
１分子中に少なくとも２個のＳｉＨ基を有するオルガノ水素ポリシロキサン（Ｂ）と、
ヒドロシリル化反応によりＳｉＨ基と反応する官能基を1分子中に少なくとも１個以上とエポキシ基を１分子中に少なくとも１個以上有するイソシアヌル酸誘導体（Ｃ）と、
エポキシ基を１分子中に少なくとも１個以上有するポリブタジエン変性樹脂（Ｄ）と、
付加反応に必要な硬化触媒（Ｅ）と、から成る付加反応硬化型樹脂組成物であり、
オルガノポリシロキサン（Ａ）とオルガノ水素ポリシロキサン（Ｂ）は、
１分子中に少なくとも１個の（Ｃ６Ｈ５）ＳｉＯ３／２ 単位を有するオルガノポリシロキサン（Ａ１）から成るオルガノポリシロキサン（Ａ）と、下記組成式（I）で表される直鎖状のオルガノ水素ポリシロキサン（Ｂ１）から成るオルガノ水素ポリシロキサン（Ｂ）であるか、
（ＨＲ２ＳｉＯ１／２）ｍ（Ｒ２ＳｉＯ２／２）ｎ[Ｒのうち少なくとも１個はフェニル基であり、ｍは２、ｎは１以上の整数］ （Ｉ）
直鎖状のオルガノポリシロキサン（Ａ２）から成るオルガノポリシロキサン（Ａ）と、１分子中に少なくとも１個の（Ｃ６Ｈ５）ＳｉＯ３／２単位を有するオルガノ水素ポリシロキサン（Ｂ２）から成るオルガノ水素ポリシロキサン（Ｂ）である、
ことを特徴とする付加反応硬化型樹脂組成物。 Organopolysiloxane (A) having two or more alkenyl groups in one molecule that react with SiH groups by hydrosilylation reaction;
An organohydrogenpolysiloxane (B) having at least two SiH groups in one molecule;
An isocyanuric acid derivative (C) having at least one functional group that reacts with SiH groups by hydrosilylation reaction in one molecule and at least one epoxy group in one molecule;
A polybutadiene-modified resin (D) having at least one epoxy group in one molecule;
An addition reaction curable resin composition comprising a curing catalyst (E) necessary for the addition reaction,
Organopolysiloxane (A) and organohydrogenpolysiloxane (B) are:
Organopolysiloxane (A) composed of organopolysiloxane (A1) having at least one (C 6 H 5 ) SiO 3/2 unit in one molecule, and a straight chain represented by the following composition formula (I) Or an organohydrogenpolysiloxane (B) comprising the organohydrogenpolysiloxane (B1) of
(HR 2 SiO 1/2 ) m (R 2 SiO 2/2 ) n [At least one of R is a phenyl group, m is 2, and n is an integer of 1 or more] (I)
Organopolysiloxane (A) composed of linear organopolysiloxane (A2) and organohydrogenpolysiloxane (B2) having at least one (C 6 H 5 ) SiO 3/2 unit in one molecule An organohydrogenpolysiloxane (B),
An addition reaction curable resin composition characterized by the above.
An optical semiconductor device, wherein an optical semiconductor element is sealed with a cured product of the addition reaction curable resin composition according to any one of claims 1 to 5.
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| KR20200128540A (en) * | 2018-03-08 | 2020-11-13 | 다우 실리콘즈 코포레이션 | Self-adhesive silicone elastomer |
| JP2021536519A (en) * | 2018-08-31 | 2021-12-27 | ワッカー ケミー アクチエンゲゼルシャフトWacker Chemie AG | Curable organopolysiloxane compositions, encapsulants and semiconductor devices |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20200128540A (en) * | 2018-03-08 | 2020-11-13 | 다우 실리콘즈 코포레이션 | Self-adhesive silicone elastomer |
| JP2021520421A (en) * | 2018-03-08 | 2021-08-19 | ダウ シリコーンズ コーポレーション | Self-adhesive silicone elastomer |
| JP7089042B2 (en) | 2018-03-08 | 2022-06-21 | ダウ シリコーンズ コーポレーション | Self-adhesive silicone elastomer |
| KR102477328B1 (en) | 2018-03-08 | 2022-12-15 | 다우 실리콘즈 코포레이션 | Self-adhesive silicone elastomer |
| JP2021536519A (en) * | 2018-08-31 | 2021-12-27 | ワッカー ケミー アクチエンゲゼルシャフトWacker Chemie AG | Curable organopolysiloxane compositions, encapsulants and semiconductor devices |
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